Short-chain hydrocarbons produced from the pyrolysis of frying oil

Description

/ 14 Short-chain hydrocarbons produced from Pyrolysis of frying oil Invention field

[001] SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL refers to a mixture of light hydrocarbons obtained through the catalytic pyrolysis process (using heated steam) of residual frying oil using commercial zeolite, representing an important alternative for utilizing and adding value to the waste by transforming it into a process raw material. The great importance of this research is associated with environmental aspects, with the proper disposal and / or use of frying oil, as well as the economic aspect, with the issue of generating new types of fuels in Brazil. Theoretical basis

[002] Fuel prices have been rising in recent years due to declining fossil fuel production. Fossil fuel shortages are predicted to arrive in less than a century. In addition, global warming has been a major problem worldwide. Thus, many countries are mobilizing to reduce carbon dioxide emissions, aiming for carbon neutrality by 2030.

[003] Renewable biofuel is a good substitute for fossil fuels to reduce carbon dioxide emissions. Currently, biofuels have been used in many applications, especially for transportation. Many studies are being developed for the conversion of waste oil and fat into biofuels, mainly using thermochemical processes, among which pyrolysis and transesterification stand out. Petition 870250004552, dated 01 / 21 / 2025, page 12 / 34 / 14

[004] Waste cooking oil is oil generated after the frying process in kitchens, restaurants, and catering industries. Frying oil consists of triglycerides (> 90%) and fatty acids, and is contaminated by some byproducts during the frying process. The consumption of fried foods results in the generation of a large volume of oils, which are considered solid waste with high polluting potential. More than 200 million liters of used vegetable oils per month are discharged untreated into rivers and lakes, compromising the environment. Today, oil is the biggest pollutant of fresh and salt water in the most densely populated regions of Brazil.

[005] Among the many products that are difficult to degrade in the environment are oils and fats, such as olive oil, vegetable oil, lard, and others. These substances do not dissolve or mix with water, forming a dense layer on the surface that prevents gas exchange and oxygenation, becoming a problem for rivers, lakes, and aquifers. Fats also negatively interfere with sewage treatment, and pipe blockages are common. The clogging of the network forces sewage to infiltrate the soil, contaminating the water table, or reaching the surface. To remove the oil and unclog the pipes, highly toxic chemicals are used, which ends up creating a pernicious cycle. In addition to causing irreparable damage to the environment, it constitutes an illegal practice punishable by law.

[006] Chemical and biological technologies have been adopted to convert waste frying oil into biofuels. Among them, catalytic pyrolysis is a fast method for depolymerizing biomass constituents at a very high heating rate in the temperature range of 400-600 °C in the absence of oxygen. Catalytic pyrolysis of this type of material can produce value-added compounds, including light hydrocarbons with short carbon chains (C8 to C13), benzene, toluene, and xylenes.

[007] Bio-oil obtained during the pyrolysis of frying oil, without the use of a catalyst in the process, is quite unstable, and may undergo polymerization and condensation over time. One of the undesirable characteristics of bio-oil is its low thermal stability, caused by the reactivity of many of the compounds. Petition 870250004552, dated 01 / 21 / 2025, page 13 / 34 / 14 present in the oil, which during storage can react with each other forming larger molecules and consequently cause changes in the physicochemical properties of the oil, such as increased viscosity. Acidity and high levels of oxygenated compounds promote the polymerization of compounds and consequently the aging of the bio-oil.

[008] To convert frying oil into stable, high-quality biofuel oil, several strategies need to be addressed, including the search for and development of new catalysts. Due to their high thermal stability and catalytic capacity, the zeolite group has been widely used as a catalyst in biomass gasification processes to reduce tar formation during cracking and reforming processes of high molecular weight compounds, as well as producing higher yields of aliphatic hydrocarbons with short carbon chains and light aromatics. The use of zeolites in catalytic pyrolysis tests promotes the production of biooil with oxygen-free compounds and a pH close to neutrality.

[009] Research into the application of the catalytic pyrolysis process of residual frying oil to obtain biofuels shows itself as an important alternative for utilizing and adding value to the waste by transforming it into a process raw material. The great importance of this research is associated with environmental aspects, with the proper disposal and / or use of frying oil, as well as with the economic aspect, with the issue of generating new types of fuels in Brazil. State of the Art

[011] Document CN108129270B presents the invention of a method for preparing phenolic substances by catalytic pyrolysis of biomass using nitrogen-impregnated carbon, comprising the following steps: grinding and drying the biomass and then carrying out fast pyrolysis in ammonia gas to obtain a nitrogen-impregnated carbon catalyst that has developed porosity and is rich in active nitrogen-containing functional groups; a large Petition 870250004552, dated 01 / 21 / 2025, page 14 / 34 / 14 A quantity of phenolic substances with high added value can be obtained using nitrogen-doped carbon catalyst to catalyze and pyrolyze biomass. The nitrogen-impregnated carbon catalyst is used as a catalyst and hydrogen donor in the catalytic pyrolysis process, so that the formation of simple phenolic substances with high added value is greatly promoted.

[012] Catalyst compositions and their use in the catalytic pyrolysis of biomass, document AU2017279755B2 is an invention that discloses a catalyst useful for catalytic pyrolysis of biomass, said catalyst being constituted by: (i) matrix material comprising a support and / or binder, and (ii) at least one metal oxide in the matrix material, wherein the metal oxide comprises metal selected from the group consisting of tungsten, chromium, cobalt, molybdenum, nickel and combinations thereof.

[013] Published on 01 / 08 / 2008, document US8202332B2 (Fractional catalytic pyrolysis of biomass) presents methods for fractional catalytic pyrolysis that allow the conversion of biomass into various desired products without the need for post-pyrolysis separation. The methods involve the use of a fluid catalytic bed that is maintained at a suitable pyrolysis temperature. Biomass is added to the catalytic bed, preferably while entrained in a non-reactive gas, such as nitrogen, causing the biomass to be pyrolyzed and forming the desired products in vapor and gas forms, allowing the desired products to be easily separated.

[014] Document BR 11 2022 021041 8 A2 (Methods for the production of crude bio-oil) shows that when the thermochemical liquefaction of lignocellulosic biomass is carried out using recirculated product oil as a solvent, the yields can be substantially increased by the addition of a short-chain alcohol reagent such as ethanol or methanol. A synergistic effect is thus obtained when liquefaction is improved compared to the use of recycled product oil or alcohol alone. The combination of recirculated product oil and alcohol reagent allows high Petition 870250004552, dated 01 / 21 / 2025, page 15 / 34 / 14 conversion at considerably lower operating pressures than normally applied in alcohol solvolysis, typically within the range of 30 to 60 bar. The liquefaction reaction occurs due to subcritical pressure where the alcohol acts as a gaseous reagent and not as a solvent.

[015] Published on 01 / 17 / 2023, document BR 11 2022 017597 3 A2 (Method of supplying a bio-oil to a hydrodeoxygenation reactor) presents a method for hydrodeoxygenation of a bio-oil over a catalyst bed in a hydrodeoxygenation reactor, the method including the combination of a two-phase diluent having a water dew point and a bio-oil at a bio-oil temperature that is 50°F (10°C) lower than 50°F (10°C) higher than the water dew point. The two-stage diluent includes a liquid phase and a vapor phase, where the liquid phase includes a hydrocarbon and the vapor phase includes hydrogen and water.

[016] Process for producing olefin-containing products by thermal steam cracking (BR 11 2015 010348 0 A2) refers to a process for producing olefin products by thermal steam cracking of a first furnace charge of hydrocarbons in at least one first cracking furnace (2) and a second furnace charge of hydrocarbons in at least one second cracking furnace (1), wherein the first furnace charge in at least one first cracking furnace (2) is at least partly converted into a first product stream (F) and the second furnace charge in at least one second cracking furnace is at least partly converted into a second product stream, wherein, from the first product stream (F), a first pyrolysis oil (P) is obtained and at least partly chemically processed.The first pyrolysis oil (P), downstream of chemical processing, is supplied at least in part as returned furnace charge (P') in at least one first cracking furnace (2), and at least one first cracking furnace (2) and at least one second cracking furnace (1) are operated under different cracking conditions. Petition 870250004552, dated 01 / 21 / 2025, page 16 / 34 / 14

[017] The green patent (BR 11 2022 024686 2 A2), entitled “Catalytic and continuous thermochemical process for the production of valuable derivatives from organic materials and waste”, deals with a new liquid-liquid extraction process of a bio-oil obtained by an improved thermochemical process. This extraction process gives rise to two distinct phases: an organic phase, bio-oil with added energy value, and an aqueous phase where chemical compounds with added value can be obtained: lactic acid, formic acid, hydroxymethylfurfural, furfural, levulinic acid, monosaccharides, disaccharides and compounds with antioxidant properties, among others.

[018] Published on 02 / 03 / 2021, patent application number BR 11 2020 024185 7 A2 (Hydrodynamic cavitation process for protecting catalytic processes used to deoxygenate complex mixtures of naturally occurring fats and oils into oxygen-free hydrocarbons) addresses the production of high-value biochemical products, in particular, bioparaffin, bio-LPG, bionaphtha, biojet and biodistillates in an integrated biorefinery of complex mixtures of naturally occurring fats and oils. The present invention discloses a process for the production of such biochemical products from naturally occurring oil(s) containing acyl-containing compounds having 10 to 24 carbons, including fatty acid esters and free fatty acids, and other components including impurities. The naturally occurring oil(s) is refined prior to treatment in a hydroprocessing step.The refinement method used in the present invention includes hydrodynamic cavitation to remove impurities that could deteriorate the subsequent hydroprocessing step.

[019] Patent number PI 0715873-4 A2 entitled Process for fluid catalytic cracking of oxygenated hydrocarbon compounds, published on 08 / 13 / 2013, discloses a process for fluid catalytic cracking of oxygenated hydrocarbon compounds such as glycerol and bio-oil. In the process, the oxygenated hydrocarbon compounds are contacted with a fluid cracking catalyst material for a period of less than 3 seconds. In a preferred process, a crude oil-derived material, such as VGO, is also contacted with the catalyst. Petition 870250004552, dated 01 / 21 / 2025, page 17 / 34 / 14

[020] The publication Improved Fast Catalytic Pyrolysis Process (application number BR 11 2017 010285 4 A2, dated 02 / 14 / 2018) presents an improved fast catalytic pyrolysis process comprising the steps of: a) feeding biomass, a specific catalytic composition of a carrier fluid to a fast catalytic pyrolysis process fluidized bed reactor maintained under reaction conditions to manufacture a crude fluid product stream, b) feeding the crude fluid product stream from step a) to a catalyst extraction and separation system to produce separate catalyst and a fluid product stream, c) feeding the fluid product stream from step b) to a vapor / liquid separation system to produce a liquid phase stream and a vapor phase stream comprising benzene, toluene and xylenes, d) feeding the vapor phase stream from step c) to a product recovery system to recover benzene, toluene and xylenes,ee) recycle at least a portion of the toluene recovered from step d) to the fluidized bed reactor from step a). Unique selling point of the invention A prior art search was conducted to verify the existence of methodologies similar to that employed in the invention "SHORT CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL". The use of heated water vapor as a carrier gas is the major differentiating factor of this invention compared to others found during the prior art search. The heated water vapor, used during the catalytic pyrolysis of residual oil in this invention, is able to direct the vapors formed during the thermal degradation of the material to the reactor outlet, thus avoiding secondary reactions and consequently the grouping of these organic compounds into structures with higher molecular weight. Description of the invention

[021] This part of the descriptive report will present the following parts of the present invention: SHORT CHAIN ​​HYDROCARBONS PRODUCED BY Petition 870250004552, dated 01 / 21 / 2025, p. 18 / 34 / 14 This study, based on the pyrolysis of frying oil, is as follows: (a) catalytic pyrolysis step of frying oil, (b) physicochemical analyses of the bio-oil obtained during the catalytic pyrolysis of frying oil, and (c) advantages of the bio-oil obtained in the research. The used oil was collected from a fast-food chain in the city of Palmas, Tocantins. The residual cooking oil was characterized using classical and instrumental methodologies (Ash, Volatile Matter, Fixed Carbon) and elemental analysis (carbon, hydrogen, nitrogen, and sulfur). The crude residual oil presented the following characteristics: (a) carbon content = 76.1%, volatile matter content = 97.4%, and ash content = 1.2%. No sulfur was detected in the residual oil, indicating the potential for energy recovery from this material.

[022] Catalytic pyrolysis step of frying oil:

[023] In this research, commercial zeolite was used as a catalyst (Fig. 1), this material being supplied by the Department of Environmental Technology of the University of Ribeirão Preto (UNAERP). For chemical characterization purposes, the material was ground in a ball mill and sieved through a sieve with a 0.59 mm opening (ABNT 30, Tyler 28). The crystalline properties of the catalyst were analyzed using X-ray diffractometry (Fig. 2). Thermal stability was determined using the TG / DTG technique (Fig. 3). The zeolite showed, through X-ray diffraction analysis, the characteristic peaks of the crystalline phase for the formula (K2O*Na2O)*Al2O3*2SiO2*nH2O.

[025] Thermal conversion was carried out in a fixed-bed stainless steel reactor, 100 cm long and 10 cm in external diameter, as shown in Fig. 4(a). The reactor was heated by a tilting split furnace. The reactor was operated in batch mode, using steam heated in an autoclave, as shown in Fig. 4(b), as the carrier gas. In all tests, the reactor was initially heated to 150°C for 30 minutes at a heating rate of 30°C / min. The product was bio-oil, as shown in Fig. 4(c). Petition 870250004552, dated 01 / 21 / 2025, page 19 / 34 / 14

[026] Initial tests were carried out operating the reactor at three different temperatures (400, 500 and 600oC), with the aim of verifying the best condition for obtaining the maximum bio-oil yield. In this stage the heating rate was 20oC / min and the catalyst mass ratio was 7% (Fig. 5).

[027] The effects of two factors on the frying oil pyrolysis system were verified through multivariate design. A Face-Centered Design (FCD) experimental design was applied, without repetitions, with 17 types of combinations between the factors. The factors studied were: pyrolysis temperature, heating rate and catalyst mass ratio (Table 1). Table 1 - Factors and levels used in the DFC experimental design Factors Levels -1 0 +1 Pyrolysis temperature (°C) 450 550 650 Heating rate (°C / min) 10 20 30 Catalyst mass ratio (%) 2 5 8

[028] For mass balance purposes, after the reaction and cooling of the pyrolysis unit, all process products, both liquid and solid, were collected and weighed. The solid material was recovered directly from the reactor and the pyrolytic liquids were collected after the vapor condensation system in a phase separation funnel.

[029] Based on the results of the experimental design, the statistical model for bio-oil production was determined using STATISTICA software, and the following were determined: (a) regression coefficients, (b) standard error of coefficients, (c) interval estimate, and (d) p-value for each coefficient.

[030] The bio-oil obtained in this study was analyzed by gas chromatography with an HP-5MS capillary column (0.25 mm x 0.25 μm x 30 m). Petition 870250004552, dated 01 / 21 / 2025, page 20 / 34 / 14

[031] Physicochemical analyses of bio-oil obtained during catalytic pyrolysis of frying oil:

[032] The highest yield of C8-C12 type hydrocarbons was 77.2% obtained under the following conditions: (a) temperature = 550°C, (b) reactor heating rate of 20°C / min and (c) catalyst mass ratio of 2%. The lowest yield of C8-C12 compounds was observed in test 6 (temperature = 650°C; heating rate = 10°C / min and catalyst mass ratio = 8%). Some of the hydrocarbons obtained in the bio-oil from waste oil pyrolysis are shown in Figure 6.

[033] Regarding the C8 - C12 yield (%), temperature had a significant effect (at the linear and quadratic levels) and the variables heating rate and catalyst mass ratio were statistically significant at the quadratic level. The interactions between the three variables are not significant at the 95% confidence level.

[034] Through linear regression, the spectral range relating the variables temperature, heating rate, catalyst mass ratio, and also the interaction between the variables for the response C8-C12 Yield (%) was generated.

[035] Based on the data from the linear regression analysis of the results obtained, it was possible to formulate a polynomial model to describe the response variable Yield C8 - C12 %. Equation 1 shows the second-order model for the variables, considering all regression coefficients for 95% confidence, disregarding the interaction terms between the variables of the experimental design. (1) Where: X1 = Temperature; X2 = heating rate; X3 = catalyst mass ratio (in coded values)

[036] Figure 7 shows the response surfaces for the yield of C8-C12 hydrocarbons (%) produced in the pyrolytic plant of this work. Fig. 7 (a) presents the data obtained taking into account the reactor temperature and the heating rate. Fig. 7 (b) shows the relationship between the reactor temperature and the mass ratio of catalyst used. Fig. 7 (c) provides the interaction between the furnace heating rate and the mass ratio of zeolite used in the Petition 870250004552, dated 01 / 21 / 2025, page 21 / 34 / 14 pyrolysis tests of frying oil. Through response surface analysis, the strong influence of temperature, heating rate, and catalyst mass ratio on the production of hydrocarbons with 8, 9, 10, 11, and 12 carbons can be verified. The red regions indicate the conditions of highest production of these types of organic compounds. The optimal production region of C8 - C12 was observed under the following conditions: reactor temperature (525 to 550°C), heating rate (16 to 22°C / min), and catalyst mass ratio (2 to 3%), under the conditions studied here.

[037] Advantages of bio-oil obtained in the research:

[038] Bio-oil is considered a renewable feedstock for the production of energy, fuels, chemicals and carbon materials. These specifically include the direct combustion of bio-oil as boiler fuel, the production of biofuel from bio-oil via hydrotreatment, the production of value-added chemicals by separation and acid catalysis / hydrogenation, or the conversion of bio-oil into carbon materials through polymerization / cracking. Considerable efforts are being made to develop a viable method through research for the utilization of bio-oil for the conversion of bio-oil into useful products.

[039] Bio-oil is one of the main products of the fast pyrolysis process, and can also be considered a promising raw material for replacing petroleum fuels for use in heating and energy. In addition, it can also be used to produce value-added chemicals.

[040] The literature cites the potential of fast pyrolysis bio-oil as an antifungal agent for wood protection, and according to reports obtained, the liquid in question can be used to treat pine wood to improve its resistance to decay and hydrophobicity, showing that an innovative use for bio-oil is possible. In this way, they also highlight that the use of biomass materials as a source of preservative compounds could be even more attractive if residual material, such as rejected wood shavings, were used. Petition 870250004552, dated 01 / 21 / 2025, page 22 / 34 / 14 an industrial paste process, but in any case the discovery of a new use for bio-oil is already considered a great advance.

[041] Studies on bio-oil derived from the fast pyrolysis of waste materials show that bio-oil can also be used as an efficient antifungal and hydrophobic agent for wood protection. Impregnation with bio-oil has also proven effective in reducing water absorption and wettability in pine forests. The bio-oil contained in pine can act as a water repellent, blocking the capillary microstructures responsible for the absorption and flow of liquids. Water absorption by pine can decrease fivefold, depending on the bio-oil content. However, the thermal stability of pine wood tends to decrease with increasing bio-oil content. In their studies, bio-oil improved resistance to decay by 2.6 times, and protection against T. versicolor and G. trabeum fungi by 4.5 times, in addition to causing the mortality of the entire fungal colony present in the first days of testing.

[042] These monomeric phenolic compounds are able to rapidly neutralize free radicals, generating stable and non-reactive products. They are also able to chelate metal ions, which are two important mechanisms for preventing fungal attack, thus generating fungicidal capacity for bio-oil and bringing a new use for it.

[043] Fast pyrolysis bio-oil can also be used as a precursor to carbon fiber. The main raw materials for carbon fiber are polyacrylonitrile and mesophasic pitch, which consist of common tar mixed with residual coal tar. Both are raw materials of fossil origin and have high processing costs.

[044] Bio-oil can also be used as a raw material for the production of various other products due to its chemical characteristics. Examples of this alternative use include candles, paints, varnishes, resins, animal feed, automotive lubricant for agricultural machinery, and soaps, but due to the high cost, studies have been limited. Petition 870250004552, dated 01 / 21 / 2025, page 23 / 34 / 14 developed, with the amount of information and characterization of the components being limited.

[045] Bio-oil is traded at $50.6 Canadian dollars per barrel. This value represents about 70% of the value of conventional crude oil traded in the country. Description of the figures

[046] Detailed descriptions of the parts of the present invention, and their respective reference numbers, are presented below: Figure 1 refers to commercial zeolite used in the catalytic pyrolysis of frying oil. Figure 2 refers to the difphogram obtained during the analysis of the commercial zeolite used in the research. Figure 3 refers to the results of the thermogravimetric analysis of the commercial zeolite used in the research. Figure 4 (a) refers to the pyrolysis reactor used in the thermal degradation of frying oil. Figure 4 (b) refers to the autoclave used in the generation of heated steam. Figure 4 (c) refers to the bio-oil condensation and collection system. Figure 5 refers to the bio-oil obtained during the catalytic pyrolysis of frying oil. Figure 6 refers to the hydrocarbons present in bio-oil. Figure 7 (a) refers to the response surface obtained with experimental data during catalytic pyrolysis of residual oil, with the variables pyrolysis temperature and furnace heating rate. Petition 870250004552, dated 01 / 21 / 2025, page 24 / 34 / 14 Figure 7 (b) refers to the response surface obtained with experimental data during catalytic pyrolysis of residual oil, with the variables pyrolysis temperature and catalyst mass ratio. Figure 7 (c) refers to the response surface obtained with experimental data during catalytic pyrolysis of waste oil, with the variables furnace heating rate and catalyst mass ratio. Petition 870250004552, dated 01 / 21 / 2025, page 25 / 34

Claims

1 / 2 CLAIMS 1. SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL, characterized by being produced by the pyrolysis process using residual frying oil, therefore constituting a green patent according to RESOLUTION No. 175 / 2016 which governs the priority examination of "Green Patent" applications.

2. Short-chain hydrocarbons produced from the pyrolysis of frying oil, characterized by being produced by the pyrolysis process with reactor temperature parameters above 500 °C and an inert atmosphere.

3. SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL, characterized by claims 1 and 2, being produced through the thermal degradation of frying oil using water vapor as a carrier gas.

4. SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL, characterized by claims 1, 2 and 3, being produced through the thermal degradation of residual frying oil with the presence of commercial zeolite for catalytic degradation of the residue. Petition 870250004552, dated 01 / 21 / 2025, page 26 / 34 2 / 2 5. SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL, characterized by claim 4, being produced through catalytic pyrolysis with ZSM-5 zeolite.

6. SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL, characterized by being produced through the catalytic pyrolysis of frying oil with bio-oil yields of 60% obtained in pyrolysis carried out at 500 °C.

7. SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL, characterized by being produced through the catalytic pyrolysis of residual frying oil with a C8-C12 hydrocarbon yield of 77.2% obtained under the following conditions: (a) temperature = 550 °C, (b) reactor heating rate of 20 °C / min and (c) catalyst mass ratio of 2%.

8. Short-chain hydrocarbons produced from the pyrolysis of frying oil, characterized by having in their chemical composition the compounds with the chemical formulas C8H14, C9H16, C10H18, C11H20 and C12H24.

9. SHORT-CHAIN ​​HYDROCARBONS PRODUCED FROM THE PYROLYSIS OF FRYING OIL, characterized by having in its chemical composition light hydrocarbons from C8 to C12, this mixture having physicochemical properties similar to diesel and can be used in the production of various objects that use petroleum as a raw material. Petition 870250004552, dated 01 / 21 / 2025, pp. 27 / 34

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