Process for producing renewable products from bio-oil and oil streams by catalytic cracking

Abstract

The present invention is in the field of fluid catalytic cracking processes (FCC) for the production of fuels with fully renewable contents, more particularly for the production of high octane gasoline (RON higher than 92 and / or MON higher than 83) and middle distillates. More specifically, the present invention relates to the co-treatment of bio-oil and oil streams in the presence of a zeolite catalyst having a mesopore size to produce more and better gasoline, reducing the amount of heavy fractions of low commercial value.

Description

Technical Field

[0001] The present invention belongs to the field of fluid catalytic cracking (FCC) processes for producing fuels with a completely renewable content, more specifically high-octane gasoline (RON (“Research Octane Number”) higher than 92 and / or MON (“Motor Octane Number” higher than 83) and middle distillates. More specifically, the present invention relates to the co-processing of bio-oil and grease streams in the presence of a zeolite catalyst with medium pore size, in order to produce more and better gasoline, reducing the amount of heavy fractions of low commercial value and eliminating the use of flare oil to balance the heat balance of the unit.

[0002] Bio-oils are produced by fast pyrolysis, catalytic pyrolysis, hydrothermal liquefaction, or other thermochemical methods for the conversion of lignocellulosic biomass. Background Art

[0003] Brazil is one of the 195 signatories of the Paris Agreement, which aims to strengthen the global response to the threat posed by climate change caused by greenhouse gas emissions. In the Agreement, each signatory established its own commitments based on the so-called Nationally Determined Contributions (or NDCs), and proposed its contribution to the reduction of greenhouse gas (GHG) emissions, thus trying to limit the increase in the global average temperature to 2.0℃ above pre-industrial levels. The commitments made by Brazil's NDC foresee a 37% reduction in GHG emissions by 2025 compared to 2005 values, and by 2030, 43% below 2005 levels. One of the ways to achieve this goal is to establish a commitment to increase the share of sustainable bioenergy in its energy matrix to about 18% by 2030. With the launch of the RenovaBio program (Law #13,576 / 2017 of December 26, 2017), a national biofuels policy was developed, among which the objectives are to promote the appropriate expansion of the production and use of biofuels in the national energy matrix and to provide predictability for the competitive participation of several biofuels in the national fuel market.

[0004] Fluid catalytic cracking (FCC) is one of the main conversion processes, present in most refineries. It is mainly used to produce high octane gasoline by using zeolites that convert high molecular weight molecules into smaller molecules. Its technology is very flexible, allowing the conversion of heavy petroleum streams, and its operating conditions can be optimized for the production of products in the gasoline, propylene or diesel range. FCC units can be found in most refineries in Brazil.

[0005] In the fluidized bed catalytic cracking process, the hydrocarbon cracking reaction occurs by contacting the hydrocarbon stream with the catalyst in a tubular reactor (also called a riser) in the form of an upward flow under dynamic flow, thereby converting it into a lighter hydrocarbon stream with greater economic value. Thus, a hydrocarbon stream from petroleum refining with a boiling point of 350° C. to 550° C. is converted into lighter hydrocarbons, mainly gasoline components with a distillation range of 35° C. to 220° C. Alternatively, liquid streams from renewable sources can also be used. The reaction temperature (TRX) in the reactor is about 540° C. at the reactor outlet.

[0006] The cracking reaction is endothermic, and the increase in the severity of the reaction makes it difficult to meet this energy demand. In conventional catalytic cracking, this heat demand is met by burning the coke deposited on the catalyst in the reaction section. The catalyst is burned with air at a temperature of about 700°C in the regeneration section. In this way, its catalytic activity is reestablished, and the heated catalyst can be returned to the reaction section and provide the heat necessary for the endothermic reaction.

[0007] Modern regenerators operate in the dense phase of the regenerated bed, where the majority of the combustion of the coke deposited on the catalyst occurs, with a minimum temperature of about 680°C and a catalyst residence time of about 4 minutes in the regenerator, which ensures the combustion of the coke. Typically, the maximum design temperature in the dense phase of the bed is 760°C, while in operation this temperature is maintained at a maximum of 730°C.

[0008] The problem of meeting the heat requirement is exacerbated if the feed stream used is an oil (lipid) stream, such as soybean oil, castor oil and tallow. These renewable source streams have linear chains with up to 18 carbons in their structure, such as Figure 1 , which shows a typical triglyceride structure. The linear carbon chain typically has 9 to 18 carbon atoms. These streams typically contain at least one unsaturation and have a low potential for coke formation in catalytic cracking.

[0009] The grease stream cannot be used directly as a fuel but can be converted into higher value-added products such as jet fuel, diesel and BTX aromatics (benzene, toluene and xylenes).

[0010] Catalysts that can be used for catalytic cracking include Y zeolites of USY and REY types. In commercial catalytic cracking reactors, ZSM-5 zeolites (MFI) with medium pore size are also used to produce olefins, aromatics and to improve the octane number of gasoline. The term "medium pore size zeolite" is applicable to any zeolite that has a medium pore size relative to small pore zeolites (e.g., A-type zeolites) and large pore zeolites (e.g., X zeolites and Y zeolites). Medium zeolites are crystalline structures whose rings contain 10 or 12 oxygen atoms. These zeolites must have a silicon-aluminum ratio of 10 to 300. Except for ZSM-5, examples of medium pore zeolites are zeolites ZSM-8, ZSM-11 (also referred to as MEL), ZSM-12, ZSM-21, ZSM-23, ZSM-35, ZSM-38, IMF (also referred to as IM-5), TUN (also referred to as TNU-9) and EUO.

[0011] Catalysts based on ZSM-5 are essential for the cracking of oxygenated compounds of oil and fat streams and the conversion of these compounds into hydrocarbons. The article "Catalytic cracking of mixtures of model bio-oil compounds and gas oil" shows that there is a preferential interaction between ZSM-5 and oxygenated compounds, resulting in a greater removal of oxygen from the reaction products ( I; RIBEIRO, F.; CERQUEIRA, HS; LAM, YL; DE ALMEIDA, MBB; Catalytic cracking of mixtures of model bio-oil compounds and gasoil. Applied Catalysis B: Environmental. 90(3-4):556 to 563 (2009)).

[0012] However, the processing of grease streams in catalytic cracking results in their heat demand not being met due to two main reasons: 1) the feedstock used is not itself a good precursor for coke formation, showing low Ramsbottom carbon residue; 2) ZSM-5 zeolite and other zeolites with smaller cavities than zeolite Y do not produce large coke deposits on the catalyst.

[0013] However, there is almost no literature on solving the problem of insufficient energy in catalytic cracking. Usually, this deficiency is solved by burning combustion oil (also called heating oil) in the regenerator. According to this method, the regenerator becomes a burner, in which the oil combustion produces enough heat to heat the catalyst. The regenerator bed must be heated to a temperature of about 700°C by burning the combustion oil. The dense phase temperature (DPT) below 680°C makes it difficult to burn heating oil in the regenerator bed and leads to uncontrolled catalyst circulation towards the cracking reactor. The heat generated is transmitted to the reaction section by the catalyst itself. However, burning oil in the regenerator bed promotes the emergence of several problems in the operation of the regenerator. For example, since heating oil with a very low distillation point may cause late combustion, that is, combustion outside the bed, the selection of heating oil to be used must be cautious. The temperature difference between the bed and the combustion gas can reach 300°C, thereby generating high temperatures in the cyclone separator and other equipment inside and outside the regenerator. Another possible problem is the wear of the disperser responsible for introducing heating oil into the regenerator. Due to the generation of high temperature points in the combustion bed, early deactivation of the catalyst may also occur. Furthermore, burning oil generates energy waste, which significantly increases the carbon footprint in the catalytic cracking unit. Furthermore, burning oil may increase the presence of sulfur content in the fuel produced in the FCC.

[0014] Therefore, the treatment of the grease stream in the catalytic cracking unit leads to an imbalance in the unit balance, limiting the amount of renewable stream added to the converter. A solution to this technical problem is therefore necessary.

[0015] One method of alleviating the energy deficit resulting from the use of streams with low coke formation potential consists in using in catalytic cracking a catalyst comprising a zeolite modified with a dehydrogenation metal, such as nickel, which promotes coke formation, as taught in document WO2010023456. Although the energy deficit in cracking is alleviated, the proposed solution does not eliminate it. Furthermore, the document does not propose the production of 100% renewable compounds, but rather the production of olefins.

[0016] Document US 7540952 teaches how to co-treat a grease stream with heavy vacuum diesel in catalytic cracking to maximize middle distillates. An example is the use of castor oil (castor oil or ricinus oil) as a feed for an FCC pilot unit, using a reaction temperature of 300°C to 400°C, which is much lower than the temperature used in conventional FCC. Under these conditions, products within the diesel range are maximized, but with the production of less low-octane gasoline. However, the patent does not teach how to handle the growing energy deficit caused by using a larger amount of vegetable oil as a feed for an FCC converter instead of vacuum diesel, which limits the use of this renewable fraction, and therefore does not disclose the production of 100% renewable fuels with low sulfur content.

[0017] Document BR 102014022366-5 also uses a renewable fat stream to produce cracked naphtha using a faujasitic catalyst in a catalytic cracking reactor. The produced naphtha has properties similar to those of cracked naphtha of fossil origin with a high content of bioaromatics (which has the advantage of having a low oxygenate content), giving these products a high calorific value when compared with alternative products such as ethers (ETBE and MTBE) and alcohols (ethanol and butanol). However, this document does not propose a solution to the energy deficiency in catalytic cracking caused by the use of fat streams, nor does it propose the production of 100% renewable fuels. In addition, document BR 102014022366-5 also indicates the need for an oxidation treatment step of the formed naphtha to adjust the sulfur content to less than 10 ppm and the benzene content to less than 1%.

[0018] However, some renewable streams, even liquids, have chemical properties very different from those of oil and fat streams and have a high potential for coke formation. Among these, lignocellulosic streams, such as pyrolysis oil or bio-oil produced by the rapid pyrolysis process of biomass, can be mentioned. Bio-oil is composed of a mixture of oxygenated compounds (such as aldehydes, ketones, and phenolic compounds) of several families. It has a high aromatic content and a high potential for forming coke in catalytic cracking and should not be confused with lipid streams. Document BR 102016003995-9 discloses a method for obtaining biofuels, particularly high-octane gasoline, by co-processing a gaseous stream of light saturated hydrocarbons containing pyrolysis oil (bio-oil), hydrogen-rich, and a raw material of a major fossil raw material in an FCC process. It uses two reaction sections in its process: the reaction temperature is in the range of 500°C to 800°C in the first reaction section, and in the range of 500°C to 620°C in the second reaction section. The bio-oil (plant stream) described in the document does not produce energy deficiency in catalytic cracking because it is a lignocellulose source and shows a high potential for coke formation. Therefore, unlike the present invention, the bio-oil stream must be introduced into the riser reactor separately because it is not miscible with the main (fossil) raw material. In addition, the document is not intended to produce 100% renewable compounds. In this particular case, bio-oil is introduced before the diesel input to minimize the coke yield. When bio-oil is introduced after the reference diesel input, the coke yield is maximized.

[0019] Document BR 1120170232529 combines hydropyrolysis with a hydrotreatment step for producing fuel from lignocellulosic biomass. However, the aforementioned document does not propose the catalytic cracking of bio-oil. Therefore, the invention described in patent BR1120170232529 relates to the direct hydrogenation of the bio-oil obtained by hydropyrolysis using the gas stream produced during the use process. This method shows the following economic disadvantages related to the quality of bio-oil (high water content, acidity and carbon residue): in addition to the high hydrogen consumption of the process, it also requires high severity, which has an impact on reactor engineering. Therefore, the present invention brings such progress: bio-oil can be introduced into catalytic cracking without the inconvenience caused by the hydrogenation process.

[0020] Therefore, there is no solution in the prior art that allows to produce completely renewable products in catalytic cracking at thermal equilibrium. The solutions proposed in the prior art for the production of renewable compounds lead to thermal insufficiency of the converter as the percentage of grease streams in the feed increases. In order to solve the mentioned problem, the present invention has been developed, which proposes to introduce a fraction of bio-oil produced by thermochemical biomass conversion technologies (such as fast pyrolysis or slow pyrolysis) into the catalytic cracking of grease streams for the production of 100% renewable fuels with a sulfur content of less than 10 ppm.

[0021] The aforementioned process thus allows the production of 100% renewable fuels with a sulfur content less than 10 ppm and balancing the heat balance of the FCC unit, eliminating the use of combustion oil, thus maintaining the economy and energy efficiency of the process.

[0022] In this context, the present invention proposes to produce 100% renewable fuels from abundant raw materials such as lignocellulosic biomass (eg sugar cane straw and bagasse).

[0023] The present invention is applicable to catalytic cracking units, where using lipid streams as well as fractions of streams originating from thermochemical conversion of lignocellulosic materials (e.g. pyrolysis bio-oil (fast or slow), fractions from catalytic pyrolysis or hydrothermal liquefaction), the full sustainability of FCC can be achieved, thus increasing the market revenue potential of this route due to the huge availability of lignocellulosic raw materials. Summary of the invention

[0024] As a forewarning, it is emphasized that the following description will be based on preferred embodiments of the present invention. However, as is obvious to anyone skilled in the art, the present invention is not limited to these specific embodiments, but only to the scope of protection defined in the claims.

[0025] The present invention relates to a catalytic cracking process for producing fully renewable fuels, using fat streams and bio-oil fractions as feedstocks, characterized in that these renewable streams are co-processed in fluid catalytic cracking in contact with a zeolite catalyst having a medium pore size.

[0026] The present invention produces products in the high octane MON and RON gasoline range suitable for use in Otto cycle engines. Products produced by the present invention in other distillation ranges provide fuels with lower carbon emissions to the atmosphere and sulfur content less than 10 ppm, i.e., having the desired properties for bunkers (marine fuel oils), Otto cycle engine fuels, and diesel cycle engine fuels.

[0027] The invention also aims to develop a process capable of converting streams of renewable origin into products that can be incorporated into the fuel pool but have low carbon emissions.

[0028] The invention can be applied to any existing catalytic cracking unit, provided that minor modifications are made to the feed system of the unit, ensuring that the bio-oil is injected into the unit in isolation, or even mixed with the grease stream just before entering the reactor.

[0029] The present invention provides a solution to the energy deficit caused by the use of grease streams in catalytic cracking by using bio-oil, whose high coke production potential rebalances the heat balance of catalytic cracking, eliminating the use of combustion oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The invention will now be described in more detail with reference to the accompanying drawings, which represent examples of its implementation in a schematic manner and without limiting the scope of the invention. The drawings include:

[0031] - Figure 1 The chemical structure of a typical grease stream is shown;

[0032] - Figure 2 A block diagram of the method of the invention is shown in a simplified manner. DETAILED DESCRIPTION

[0033] The present invention relates to a process for producing fully renewable fuels, in particular gasoline and middle distillate streams, by fluid catalytic cracking of a load comprising a grease stream of renewable origin and bio-oil.

[0034] The term "bio-oil" as used herein is defined as "the product obtained from the thermochemical conversion of lignocellulosic biomass having a lignin content greater than 20% by mass".

[0035] Among the plant biomasses that can be used for the production of bio-oil, mention may be made of forestry residues such as those from the paper and cellulose industry, agricultural residues such as bagasse and sugar cane straw.

[0036] The fat stream used as a load may be selected from vegetable oil streams and animal fats.

[0037] According to the invention, the feeding of a grease stream (a feed with low coke production potential) into the catalytic cracking unit is compensated by the use of bio-oil (a feed with high coke production potential). This combination allows the heat balance to be balanced during cracking, eliminating the need for burning oil. An air preheating furnace, which heats the air fed to the regeneration section, would be an additional alternative to the use of burning oil. It is usually used in cracking units only during the start-up of the unit after a maintenance shutdown. However, like burning oil, it increases the carbon footprint of the process, since it uses a fossil stream in the furnace to generate heat, raising the temperature of about 220°C at the compressor outlet to a temperature of about 500°C at the regeneration bed inlet.

[0038] The present invention also allows the production of gasoline containing high levels of aromatic compounds such as benzene, toluene, xylenes, alkylated phenols and furans.

[0039] The following uses Figure 2 Describing the present invention in detail, Figure 2 A block diagram of the process in a fluid catalytic cracking unit for treating grease and bio-oil streams, aiming at producing fuels with 100% renewable characteristics, is presented in a simplified manner.

[0040] Using steam 3 and 4 as auxiliary fluids for atomization, the grease stream 1 and the bio-oil 2 are introduced into the fluidized catalytic cracking reactor 5 in this order, thereby contacting with the zeolite catalyst 15 having medium pores from the regenerator 12. The catalyst is lifted toward the reaction zone by lifting steam 16. The feed and the catalyst are contacted under the following conditions: contact time in the range of 1.0 seconds to 3.0 seconds; catalyst to oil ratio of 5 to 30, pressure in the range of 200 kPa to 400 kPa, reaction temperature of 400° C. to 520° C.

[0041] At the reactor outlet, at the end of the reaction, the coke-deactivated catalyst 6 is separated from the products of the cracking reaction.

[0042] The coke-deactivated catalyst 6 enters a rectification stage 10 in which it receives a stream of inert gas 9, preferably water vapour, to remove light hydrocarbons 8 which are directed to mix with the products already separated, constituting the hydrocarbon stream 7 obtained in the process.

[0043] After the rectification 10, the deactivated catalyst 11 enters a regeneration stage 12 by burning the coke in the presence of air 13, thereby obtaining a combustion gas 14 whose main components are carbon monoxide, carbon dioxide, nitrogen and unreacted oxygen.

[0044] The regenerated catalyst 15 is returned to the reactor 5 at a temperature high enough to provide heat for the endothermic reaction of the process, thereby completing the cycle of the process of the present invention.

[0045] The hydrocarbon stream 7 obtained in the process comprises: fuel gas (hydrogen, C1 and C2) including ethylene, lights (C3 and C4); naphtha (C5+, 220°C); intermediate products (220°C, 344°C) and bottom products (>344°C).

[0046] The feed oil and fat stream 1 of the present invention can be a plant or animal-derived biomass composed of monoglyceride, diglyceride or triglyceride, wherein the oil from a renewable source can be castor oil, soybean oil, cottonseed oil, tallow, or any other triglyceride or its transesterification reaction product with methanol or ethanol.

[0047] In an alternative embodiment of the invention, the grease stream 1 is mixed with the bio-oil 2 in Figure 2 The mixture is mixed in a mixer not shown.

[0048] The zeolite catalyst having an intermediate pore size includes a crystal structure selected from the group consisting of MFI, MEL, ZSM-8, ZSM-12, ZSM-21, ZSM-23, ZSM-35, ZSM-38, IMF and TUN, and any combination of these.

[0049] A typical catalyst comprises 10% w / w to 75% w / w of a zeolite having a medium pore size, 1% w / w to 40% w / w of alumina, 0% w / w to 20% w / w of silica, 0% w / w to 20% w / w of phosphorus; and kaolin for blocking the balance.

[0050] The fluid catalytic cracking reactor is a riser type.

[0051] The gasoline produced can then be hydrogenated at a temperature of 350 to 390° C. using a sulfide system based on CoMo / Al 2 O 3 (containing 2.5 to 6% by mass of cobalt and about 7 to 10% by mass of molybdenum) as catalyst.

[0052] The present invention also allows for the production of middle distillates intended for use in the production of renewable diesel or as fuel oil.

[0053] Thus, in a first embodiment, the present invention relates to a method for producing a wide range of renewable products having qualities suitable for incorporation into a renewable diesel pool, or for use as a renewable fuel oil, or even for incorporation into a renewable gasoline pool, the method comprising the steps of: (a) mixing a grease stream with a bio-oil, and (b) converting the mixture in a catalytic cracking process.

[0054] The invention also describes a method for obtaining a renewable fuel by combining two different renewable loads: bio-oil and a grease stream. It should be noted that the bio-oil comes from a lignocellulosic biomass conversion process, such as pyrolysis or hydrothermal liquefaction, or even a mixture of bio-oils obtained by these pathways. The biomass used to produce the bio-oil can be, in particular, sugarcane straw and bagasse.

[0055] In a second embodiment, the invention contemplates the formulation of renewable diesel for diesel cycle engines, renewable fuel oil, renewable gasoline for Otto cycle engines, comprising converting a stream comprising oleaginous compounds and bio-oil in catalytic cracking according to the above method.

[0056] The present invention will be better understood through a brief description of its embodiments.

[0057] Example:

[0058] For this study, the following tests representing examples of the invention were performed, in which the results obtained in catalytic cracking by the prior art and the invention are shown.

[0059] A set of experiments was performed over a range of process variables of interest, allowing understanding of the influence of the main variables on the results obtained.

[0060] Example 1: Yields from processing heavy vacuum gas oil and co-processing of bio-oil with heavy vacuum gas oil.

[0061] 1.1 – Feed Flow:

[0062] In the experiment, bio-oil produced from pine wood, the characteristics of which are shown in Table I, was co-processed with heavy vacuum gas oil. Another test in which pure heavy vacuum gas oil was processed was used as a reference, as shown in Table II.

[0063] Table I

[0064] Characterization of bio-oil

[0065]

[0066]

[0067] Table II

[0068] Characterization of Heavy Vacuum Diesel Oil

[0069] Heavy vacuum diesel Density 20 / 4 0.9409 API 18.3 Sulfur, mg / kg ASTM D 5453 0.65 Total nitrogen, mg / kg ASTM D 5762 0.26 Basic nitrogen, mg / kg N-2373 1312 Aniline point, ℃ NBR-11343 84.9 RCR, weight % ASTM D 4530 1.92

[0070] 1.2-Analysis:

[0071] The following yield groups are defined: fuel gas (methane, hydrogen, ethane and ethylene), LPG (C3 and C4 hydrocarbons, except propylene), propylene, naphtha (C5-220°C), LCO (220°C to 343°C), bottoms (+343°C), coke, carbon monoxide, carbon dioxide and water.

[0072] The coke yield is calculated from the mass flow rate of the combustion gas and its chromatographic composition.

[0073] Typically, studies in the literature calculate the produced water by the difference between 100 wt% and the sum of the other yields, or do not report at all how the water yield was calculated. In this example, the water yield was estimated by summing the water calculated at the end of each experiment subtracted from the amount fed to the units (lifting, dispersion, rectification and separation).

[0074] 1.2-Test Unit:

[0075] A demonstration scale FCC unit (U-144) operating at a load flow of 120 kg / hour was used. The catalyst inventory of this unit is very high, about 300 kg. The unit has an adiabatic temperature control system for the following major equipment: riser reactor, rectifier and regenerator, which allows studies involving energetic aspects of the process to be performed.

[0076] As taught in document BR 102016003995-9, the bio-oil is injected after the introduction of the heavy vacuum gas oil, which is the most suitable case to maximize the coke yield in the unit.

[0077] Based on the tested yields with reference diesel (A1) and co-treatment with 20% bio-oil (BO) and 80% diesel (A2), the estimated yield of pure bio-oil (A3) was calculated using equations 1 and 2:

[0078]

[0079] Since the percentages of diesel and bio-oil are 80% and 20% respectively, then:

[0080] Pure BO yield i = (co-processing yield i - GOP yield i (0.8)) / (0.2)

[0081] Equation 2

[0082] The octane numbers MON and RON obtained in the co-processing of bio-oil and diesel (A2) are higher than those obtained with diesel only (A1). It is conservatively assumed that the octane number of A3 is the same as that of A2.

[0083] Table III Operating Conditions and Efficiencies in U-144 (wt % relative to fuel loading)

[0084]

[0085]

[0086] Example 2: Yields from biodiesel processing and co-processing of biodiesel and bio-oil. 2.1 – Feed flow:

[0087] In the prior art experiments, biodiesel (fatty acid methyl esters) was used as a model molecule mainly containing fatty chains with about 18 carbon atoms, the properties of which are shown in Table IV. The bio-oil used in the experiments of the present invention was produced from pine wood, and its properties are shown in Table I.

[0088] Table IV

[0089] Characterization of Biodiesel (Oil-Based Streams)

[0090]

[0091]

[0092] 2.2-Test Unit:

[0093] The same demonstration scale FCC unit described in Example 1 was used. The total feed flow rate was maintained at 130 kg / hour. The grease stream was fed to the unit at 150°C. The riser pressure was maintained at 257 kPa, and the reaction temperature was maintained at 500°C. To maintain heat balance, the air fed to the regenerator was heated to 500°C.

[0094] 2.3-Analysis:

[0095] The following output groups are defined: fuel gas (methane, hydrogen, ethane and ethylene), LPG (C3 and C4 hydrocarbons, except propylene), propylene, naphtha (C5-220°C), LCO (220°C to 343°C), bottoms (+343°C), coke, carbon monoxide, carbon dioxide and water.

[0096] The coke yield was calculated from the mass flow of the combustion gases and their chromatographic composition. Samples of the entire liquid effluent were collected for simulated distillation (ASTM D2887).

[0097] Typically, studies in the literature calculate the produced water by the difference between 100 wt% and the sum of the other yields, or do not report at all how the water yield was calculated. In this example, the water yield was estimated by summing the water calculated at the end of each experiment subtracted from the amount fed to the units (lifting, dispersion, rectification and separation).

[0098] 2.4- Experimental results:

[0099] The results in Table V show the product yields and operating conditions used in the testing.

[0100] In the test (B1) related to the prior art, only biodiesel was used as feed for catalytic cracking. In B1, continuous use of combustion oil was required to maintain the dense phase temperature at 600°C, sufficient to provide combustion of the coke deposited on the catalyst at an appropriate rate.

[0101] In the tests (B2 to B4) related to the present invention, bio-oil (BO) was co-processed with the grease stream (BD) to ensure the thermal balance of the unit. The yields of experiments B2, B3 and B4 were calculated by equation 3 from the yields of A3 (Table III) and B1 (Table V).

[0102]

[0103] Where BO is the percentage of bio-oil in the FCC feed, and BD is the percentage of biodiesel (grease stream) in the FCC feed.

[0104] To calculate the combustion oil flow rates for experiments B2 and B3 and the regeneration temperature for B4, the heat of combustion of coke and combustion oil were considered to be 8740 kcal / kg and 10100 kcal / kg, respectively.

[0105] In test B2, 5% bio-oil was co-processed with 95% biodiesel. From the heat of combustion of coke and combustion oil in test B1 and from equation 4, the flow rate of combustion oil required to maintain the regenerator temperature at 600°C was calculated in a simplified manner.

[0106] Heat B1 (kcal / hour) = 10100. Combustion oil flow B1 + 8740.% Coke yield B1. / 100.

[0107] Total flow B1

[0108] Heat B1 = 37149 kcal / hour

[0109] Combustion oil flow rate (kg / hour) = (37149-8740.% coke yield / 100. total flow rate) / 10100

[0110] Equation 4

[0111] In test B2, it is still necessary to use a combustion oil flow rate equivalent to 1.1 kg / hour for combustion in the regenerator and maintenance of the heat balance. As taught by document BR 102016003995-9, the bio-oil injected downstream of the grease flow allows maximizing the coke yield to satisfy the heat balance.

[0112] According to equation 4, the co-processing of 9% bio-oil and 91% biodiesel (test B3) makes it possible to omit the combustion of oil to maintain the thermal balance of the unit.

[0113] Test B4 shows the results for 12% bio-oil and 88% bio-diesel. In this case, the dense phase temperature, where regeneration occurs, increases from 600°C to 611°C.

[0114] High conversions of more than 85% by weight were achieved in all cases.

[0115] The B1 tested very high MON and RON octane numbers, 96.8 and 102.1 respectively.

[0116] Table V U-144 Operating Conditions, Yields (Weight % relative to Feed), Aromatics and Phenol Concentrations

[0117]

[0118]

[0119] a - Combustion oil flow calculated with coke yield estimated by equation 3 applied to equation 4.

[0120] Example 3: Yields of soybean oil processing and co-processing of soybean oil with bio-oil in an ACE benchtop unit.

[0121] 3.1- Load:

[0122] In the experiments of the prior art, soybean oil mainly comprising a fatty chain with about 18 carbon atoms was used, and its characteristics are shown in Table VI. The bio-oil used in the experiments of the present invention is produced by pine wood, and its characteristics are similar to those shown in Table VII. Bio-oil is mixed with soybean oil at a level of 1 wt %, 5 wt %, 10 wt % and 20 wt %. In all mixtures, 1 wt % of the commercial dispersant TWEEN 80 from Sigma Aldrich is used.

[0123] Table VI

[0124] Characterization of bio-oil

[0125]

[0126] Table VII

[0127] Characterization of soybean oil (fat source stream)

[0128]

[0129]

[0130] *specification

[0131] 3.2-Test Unit:

[0132] ACE bench catalytic testing was used. For each test, the mass of catalyst used was 9 g. The total feed flow rate was maintained at 1.2 g / min for 64 seconds of injection time, which corresponds to a catalyst to oil ratio of 7.0. The grease stream was fed into the unit at 50°C. The reactor was controlled at a temperature of 500°C.

[0133] After the loading is injected, the reactor bed continues to be fluidized by nitrogen flow to remove any product adsorbed between or on the surface of the catalyst particles. This step is called catalyst distillation and lasts for about 350 seconds.

[0134] After this, part of the nitrogen flow is replaced by synthetic air, so that the coke on the catalyst surface is converted into carbon dioxide. In order to ensure that a complete combustion process occurs, the reactor outlet flow passes through a catalytic converter, which oxidizes all monoxides into carbon dioxide. The water formed is retained by a dryer and the dioxide is quantified in an infrared analyzer. The coke yield is calculated from this value. Since the activity of the catalyst is partially restored due to the removal of coke from its surface, this coke combustion phase is called regeneration.

[0135] The liquid product corresponds to a high molecular weight hydrocarbon fraction, characterized by compounds with a carbon number greater than 6 (six). In the treatment of renewable loads such as soybean oil and bio-oil, oxygenated compounds and water may also appear. The compounds leaving the reactor in the gas phase are condensed and stored in chromatography vials, which are suitable for condensers immersed in a bath at a temperature of about 15°C to prevent the formed products from volatilizing. The bath is a 1:1 mixture of water and ethylene glycol. The condenser containing the liquid is weighed and quantified by gas chromatography using an analysis known as simulated distillation, in which the products are grouped according to their boiling points corresponding to a certain range of hydrocarbons.

[0136] 3.3-Analysis:

[0137] The following yield groups are defined: fuel gas (methane, hydrogen, ethane and ethylene), LPG (C3 and C4 hydrocarbons), propylene, liquid products (naphtha, LCO, bottoms and water), naphtha (C5-220°C), LCO (220°C to 343°C), bottoms (+343°C), coke, carbon monoxide, carbon dioxide and water.

[0138] As mentioned above, the coke yield is calculated from the mass flow rate of the combustion gases and their chromatographic composition.

[0139] Samples of the entire liquid effluent were collected for simulated distillation (ASTM D2887).

[0140] Typically, studies in the literature calculate the water produced by the difference between 100 wt% and the sum of the other yields, or do not report how the water yield calculation was performed at all. In this example, the water yield was estimated by taking into account the oxygen present in the load (11.5 wt% in soybean oil and 57.7 wt% in bio-oil) minus the oxygen present in the CO and CO2 products.

[0141] 3.4- Experimental results:

[0142] The results in Table VIII show the product yields, gasoline compositions, and operating conditions used in the testing.

[0143] In a test related to the prior art (C1), only soybean oil was used as catalytic cracking feed and a catalyst based on a medium-pore zeolite was used.

[0144] In tests (C2 to C5) relevant to the present invention, bio-oil (BO) was co-treated with grease stream (OS) at levels of 1 %, 5%, 10% m / m and 20% m / m.

[0145] An increase in the coke content was clearly observed by adding bio-oil. When 10% bio-oil was added, the coke increased by 50%, and when 20% bio-oil was added, the coke increased by 115%. Although the increase on an industrial scale may be different, the bench-top experiments clearly show the tendency of the addition of bio-oil to contribute to the heat balance of the UFCC in grease-loaded processing.

[0146] Another very noticeable effect is the increase in the percentage of aromatics in gasoline caused by bio-oil, which increases, improving the octane number.

[0147] Table VIII Operating conditions, yields (wt% relative to loaded feed) and gasoline compositions in ACE

[0148]

[0149]

Claims

1. A method for producing renewable products from bio-oil and grease streams in catalytic cracking in a fluid catalytic cracking unit, characterized in that it comprises the following steps: (a) preheating and atomizing a renewable oil stream, and preheating and atomizing a bio-oil stream; (b) contacting the atomized stream with a regenerated catalyst comprising a zeolite having an intermediate pore size to initiate a catalytic cracking reaction; (c) separating the cracked products; (d) regenerating the catalyst by removing the coke and directing the catalyst back to the bottom of the riser to restart cracking.

2. The method according to claim 1, characterized in that the oil stream introduced into the catalytic cracking unit accounts for 70% to 98% by weight of the total load of the fluidized catalytic cracking unit, and the bio-oil derived from lignocellulosic biomass accounts for 2% to 30% by weight of the total load of the fluidized catalytic cracking unit.

3. The method according to claim 1, characterized in that the bio-oil used in the mixture is obtained via a thermochemical conversion process of lignocellulosic biomass.

4. The method according to claim 1, characterized in that the bio-oil is added at the same level point or downstream of the grease flow.

5. The process according to claim 1 , characterized in that the proportion of bio-oil of lignocellulosic origin introduced into the fluid catalytic cracking unit is between 5% and 20% by weight, and more preferably between 5% and 10% by weight, relative to the total treatment load.

6. The method according to claim 1, characterized in that the oil stream is pure or spent castor oil, soybean oil, cottonseed oil, peanut oil, tallow or other oils of vegetable origin or animal fats, or esters obtained by transesterification of these oils and fats.

7. The method according to claim 1, characterized in that the zeolite catalyst comprises 10% w / w to 75% w / w of medium pore zeolite, 1% w / w to 40% w / w of alumina, 0% w / w to 20% w / w of silica, 0% w / w to 20% w / w of phosphorus; and kaolin for sealing the balance.

8. The method according to claim 6, characterized in that the medium pore zeolite catalyst is selected from the structure types consisting of: MFI, MEL, ZSM-8, ZSM-12, ZSM-21, ZSM-23, ZSM-35, ZSM-38, IMF and TUN and any combination of these.

9. The method according to claim 1, characterized in that the fluidized catalytic cracking reactor corresponds to the following operating conditions: pressure of 200 kPa to 400 kPa, catalyst / biomass ratio in the range of 5 to 30, contact time of 1 second to 3 seconds.

10. A renewable naphtha obtained according to the method defined in claim 1, characterized in that it comprises a typical gasoline distillation range with an initial boiling point of 30°C and a final boiling point of 220°C.

11. The renewable naphtha according to claim 10, characterized by comprising 20% ​​w / w to 90% w / w of compounds with renewable aromatic rings.

12. The renewable naphtha according to claim 10, comprising less than 1% w / w oxygen.

13. The renewable naphtha of claim 10, comprising less than 10 ppm sulfur.

14. The renewable naphtha of claim 10, characterized by having a MON of at least 83 and a RON of 92.

15. A renewable middle distillate obtained according to the process defined in claim 1, characterized in that the renewable middle distillate is within the typical distillation range of LCO with an initial boiling point of 220°C and an end point of 344°C.

16. The renewable middle distillate according to claim 15, characterized by comprising less than 1% w / w oxygen.

17. The renewable middle distillate according to claim 15, characterized by comprising less than 10 ppm sulfur.

18. A renewable fuel oil obtained according to the method defined in claim 1, characterized in that the initial boiling point is 344°C.

19. The renewable fuel according to claim 18, comprising less than 1% w / w oxygen.

20. The renewable fuel oil of claim 18, comprising less than 10 ppm sulfur.

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