BR102019002908A2 - PROCESS FOR CONVERSION OF SUGAR ACETALS IN GREEN HYDROCARBONS IN THE GASOLINE RANGE, AVIATION KEROSENE AND DIESEL - Google Patents

Abstract

process for converting sugar acetals to green hydrocarbons in the range of gasoline, aviation kerosene and diesel. this invention relates to a one-step process for the production of saturated green hydrocarbons, which can be incorporated into fuels such as gasoline, aviation kerosene (qav) and diesel; and used as hydrocarbons for the most diverse applications. the green hydrocarbons produced belong to the classes of paraffins, naphthenes with alkyl and mono-aromatic substituents, whose concentrations can be controlled by the process conditions, type of catalyst, acetal / catalyst ratio and type of bio-charge. the process converts mixed isopropylenic sugar diacetals, as in a bio-oil (patent number wo2015135046 a1, where acetals are produced directly from second generation biomass), or individually (such as 1,2: 3,5-di-o -isopropylidene-ad-xylofuranose - dx). the reaction conditions occur in the presence of conventional hydrocarbons, such as n-hexane, or in their absence, under a hydrogen atmosphere (5-150 bar), temperature (100-400oc), in a fixed bed process (residence time of the a few minutes) or batch (residence times of up to 48 hours) and in the presence of bifunctional catalysts, that is, containing metallic (and bi-metallic) and acidic functions.

Description

PROCESS FOR CONVERSION OF SUGAR ACETALS IN GREEN HYDROCARBONS IN THE GASOLINE RANGE, AVIATION KEROSENE AND DIESEL Field of invention

[001] The present invention is found in the field of production of saturated green hydrocarbons, produced through renewable sources, such as sugar cane bagasse, algae, wood, elephant grass, among others. It can be applied to both conventional refinery processes and independent units. The fractions obtained from the sugar acetals can be used pure or directly mixed with the pool of conventional hydrocarbons producing in both cases gasoline, QAV and diesel. Furthermore, this process can be integrated with the concept of a biorefinery as hydrocarbons are produced from 3-5 carbons (in smaller quantities) to a main fraction containing hydrocarbons between seven and eighteen carbon atoms. Since it is possible to control the conversion of acetals in the most diverse fractions of green hydrocarbons (type and molecular weight), all types of hydrocarbon demand can be met.

Fundamentals of the Invention

[002] Despite the enormous benefits for modern civilization, the patterns of production and consumption adopted are based mostly on non-renewable sources. In addition to the continuing scarcity of these sources, the main problem stemming from their excessive use is the environmental impact on our planet, caused mainly by increases in CO2 emissions and other gases. Added to these issues are the increase in the world population and the energy demand needed to supply modern societies. In particular, the means of transport represent a large consumption of energy (approximately 25% of world demand) and are mostly dependent on fossil fuels. Among the means of transport, it is estimated a large growth expected for international air traffic, and also a 50% increase in road freight transport. In this way, aviation fuel and diesel will play a central role for the transport sector. Therefore, a paradigm shift aimed at reducing the carbon footprint without reducing energy access to people is an urgent requirement. In particular, the high potential for photosynthesis of biomass makes it eligible for the production of energy and fuel. Biomass is composed of functionalized biopolymers based on sugar and phenolic derivatives. Due to the diverse functionalities, these compounds and their derivatives are generally very reactive. On the other hand, refinery processes were designed to convert low-reactive compounds such as hydrocarbons. In fact, a conventional refinery is based on mature processes that convert a wide variety of non-renewable fillers into hydrocarbon compounds that will compose products with different specifications, such as gasoline, QAV, diesel, among others. In the coming years, one of the main challenges will definitely be to produce green fuels and use the current / conventional refinery structure. Achieving this goal will certainly shorten the path to sustainability by mitigating major environmental and health problems in addition to the production of green hydrocarbons to replace part of the oil, lowering its price. In this sense, the present invention constitutes a major advance for sustainability and is based on the conversion of sugar acetals (pure or mixed) into hydrocarbons. These compounds can be obtained, for example, directly from second generation biomass by acetalization reactions (patent number WO2015135046). Through this process, biomass is converted into a bio-oil that is chemically distinct from the biocharges reported so far. The conversion of biomass into bio-petroleum can occur in the presence of acetone (WO2015135046) or 2.5 hexadione (BR10201702297), a diketone obtained from biomass, or another organic reagent containing a carbonyl function. This reaction is flexible to the type of biomass, carbonylated reagent and it is still possible, due to the process conditions, to selectively extract the acetal derivatives of hemicellulose or cellulose (Débora Nobrega, Master's thesis, IQ-UFRJ 2017). Thus, new types of bio-oils may be processed by other processes, other than hydroprocessing, resulting in different types of products.

[003] The conversion of acetals derived from monosaccharides, such as xylose, glucose, galactose (1,2: 3,5-di-O-isopropylidene-aD-xylofuranose (C11H18O5, DX) and 1,2: 5,6- di-O-isopropylidene-aD-glucofuranose (C12H20O6, DG)) among others, pure or as bio-petroleum compounds, by typical refining processes, such as hydroprocessing, produces saturated hydrocarbons that can be used in the hydrocarbon fractions in the range gasoline, kerosene and diesel. The flexibility of both the type of renewable cargo, processing (pure or co-processed with oil) and the products obtained, makes this proposal an asset for a greener refinery and for environmental sustainability. However, until now, a process and a catalyst for obtaining Bio-QAV, object of the present invention, had not been developed.

[004] This invention shows a process for the production, mainly, of hydrocarbons specifically more concentrated in the fraction of aviation kerosene (QAV). Aviation fuel is used for commercial use (JET A and JET A-1) and for military use in turbine engine planes, produced from petroleum and composed of approximately 20% paraffins, 40% isoparaffins, 20% naphthenes and 20% mono-aromatics. Aviation fuel generally corresponds to the distillation fraction of kerosene from oil, where the temperature is between 150 and 275 ° C. Aviation biofuel can contain aromatic compounds depending on the production process used. If they do not have aromatic compounds in their composition, this can cause wear in certain types of engines, and, in addition, they are also important in sealing the engines. This type of fuel differs from traditional combustion fuels (gasoline, diesel) in that it withstands more extreme weather conditions, especially low temperatures (approximately -30 ° C). They must contain high energy density, have adequate volatility, be chemically and thermally stable, be low viscous, have a low freezing point, be non-corrosive, and must not contain particulate matter and "free" water. Usually, additives such as antioxidants are added, to improve or preserve these fuel properties. These types of fuels require standardization tests, such as the more specific ASTM (American Society for Testing and Materials) testing when compared to other fuels.

[005] There are four routes to produce aviation biofuels, also known as paraffinic synthetic kerosene (SPK): triglyceride hydroprocessing (HEFA), biomass thermochemical process (FT), biochemical conversion and fuel alcohol conversion processes. Of these, the first two routes are the most promising as alternatives to the production of petroleum-based aviation fuels. HEFA refers to the transesterification of triglycerides, that is, esters and fatty acids, extracted from plants, algae or recyclable sources, followed by hydroprocessing, from hydrodesoxygenation, hydroisomerization and hydrocracking to produce biofuel (Bio-SPK). In relation to FT there are three possible routes: pyrolysis, gasification and hydrothermal improvement, and the realization of a biomass gasification followed by a synthesis process by Fischer-Tropsh is the certified route for the production of biofuel (FT-SPK). The two processes used to produce Bio-SPK are those proposed by Neste, better known as Neste Renewable Diesel (NEXTBTL) and by UOP / Eni EcofiningTM. These two processes were initially proposed for obtaining biodiesel from vegetable oils, but by adjusting the process it is possible to produce aviation biofuel. For example, US patent 2009/0283442 A1 concerns a process developed by McCall et al. for the production of hydrocarbons in the aviation fuel range, from renewable sources such as plant and / or animal oils. The process requires a pre-treatment of the bio-oil and subsequently involves hydrogenation, decarboxylation and / or hydrodeoxygenation of the bio-oil, followed by hydroisomerization and selective hydrocracking in a single reaction step. A steam reform step can also be included to reduce hydrogen spending. This process stood out because these processes are typical of conventional refineries. In addition, the process has been approved by the ASTM (American Society for Testing and Materials) for its use as aviation biofuel production for commercial use.

[006] Strege et al. have patented (US 2013/0072731 A1) a process for producing fuel or fuel mixes from triglycerides, fatty acids and or alkyl fatty acid esters. This process consists of hydrotreating the raw material using Pd, Pt, Ni, NiMo or CoMo catalysts supported on γ-alumina. This process should take place at temperatures between 150-800 ° C and pressures of 7-70 bar. Then, the product must be subjected to cracking, isomerization and aromatization to obtain the properties of aviation fuel or other liquid fuels. In order to achieve this kerosene range, catalysts with moderate acidity and be very active for dehydrogenation and hydrogenation reactions must be used. In the examples suggested in this patent, the final product is composed mostly of n-paraffins and isoparaffins, as well as a small amount of olefins, and absence of aromatics when coconut oil and fatty acids are used. In the case of vegetable oils, the final product may also have aromatics. In general, this proposal has received prominence, as the SPK leads to less CO2 emissions than aviation fuel from fossil fuels. In addition, it has the advantage of containing very little sulfur. Because of this, the SPK has been identified by the International Air Transport Association (IATA) as the most viable alternative for replacing fossil fuels in aviation.

[007] The present invention differs from all others in that it uses sugar acetals that can be extracted from second generation biomass for the production of green hydrocarbons, but without being limited to this process of obtaining sugar acetals. In this invention, acetals, individually or mixed in the form of a bio-petroleum, are converted in the presence of light hydrocarbons to hydrocarbons in the paraffin, aromatic and naphthene classes. These grades are produced depending on the conditions of the bio-charge and the process (such as hydrogen pressure, temperature, residence time and type of catalyst). The main function of light hydrocarbon mixed with acetal is to serve as a reaction solvent, so it is recycled at the end of the process.

Summary of the Invention

[008] This invention presents a process for the production of saturated green hydrocarbons in a single reaction step that are obtained in high yield from isopropylenic sugar diacetans, pure or mixed in the form of a bio-oil (produced directly from biomass of second generation). These green hydrocarbons can be used in gasoline, diesel and QAV. It is possible to vary the reaction conditions, the type of catalyst, the charge / catalyst ratio, the reaction conditions and the type of bio-charge, thus obtaining different green hydrocarbon compositions, the main product being located in the QAV boiling temperature range. The process can take place continuously, batch or batch fed. This invention represents a step forward for the general approach of converting biomass to green hydrocarbons.

Brief description of the figures

[009] A conversion model presented in the present invention can be carried out in a fixed bed reactor. A diagram of an illustrative example is shown in Figure 1. The load is first transferred to a container (1) that will be in an inert atmosphere of N2 and a pressure of approximately 5 bar. The charge, isopropylenic diacetals derived from monosaccharides (xylose, glucose, galactose), pure or mixed in the form of a bio-oil, also containing polysaccharide acetals, in the presence of conventional hydrocarbons, having the function of solvents, is allowed in the reactor (4 ) using an HPLC pump (2). Before the reactor, a three-way valve (3) is positioned for purging and cleaning the reactor. The reactor is embedded in an oven. Next to the reactor is a condenser (5), to condense the liquid fraction. The non-condensed products pass through a pressure regulating valve, positioned after the condenser, and make up a gas stream at atmospheric pressure that is analyzed in line by a Micro-GC (6). The gas flow is calculated with the aid of a bubble meter (7).

[0010] A conversion model presented in the present invention can be performed in an autoclave type reactor with mechanical stirrer (2), as shown in Figure 2. The reactor (7) has an inlet that can be gas or liquid ( 5), a gas outlet (4) and thermocouple (3). The oven is placed around the reactor (6) and there is also a pressure gauge (1) to measure the gas in the reactor.

Detailed description of the invention

[0011] The present process uses the charge of mixtures of sugar acetals mixed with a hydrocarbon solvent. A typical example is the bio-oil (BP) derived from the ketalization process as shown in the patents (WO2015135046 A1 SANTOS, DN; MIRANDA, LSME; PEREIRA, MM; COSTA, RG; BARROS, TG; MACIEL PEREIRA, MARCELO. Process for modify second generation biomass by providing a suitable and renewable bio-oil for the refining, bio-oil and use sector. 2017, Brazil. Patent: Privilege of Innovation. Registration number: BR10201702297, title: "Process to modify second generation biomass by providing a suitable and renewable bio-oil for the refining, bio-oil and use sector ", Registration institution: INPI - National Institute of Industrial Property. Deposit: 10/24/2017). For example, the typical composition in terms of bio-petroleum acetals is shown in Table 1, and the quantitative composition of monosaccharide isopropylidene acetals is shown in Table 2, where MX and DX refer to xylose monoacetal and diacetal, respectively and MG and DG refer to glucose monoacetal and diacetal, respectively. Thus, optionally, one of the BP components can be separated, mixed with solvent and processed.

[0012] In this invention, the sugar acetal is converted by hydrogen catalytic processing under hydrogen pressure in the presence of a bifunctional catalyst: containing acidic and hydrogenating functions. Example 1 illustrates examples of such catalysts without limiting the type or quantities of those to be used. A technician can prepare and use bifunctional catalysts with similar properties to obtain product profiles that best meet his objectives. Hydroprocessing can be operated in several ways. In one of them, it can be carried out in a fixed bed reactor, as shown in Figure 1, whose description of the fixed bed process is very similar to the claim. Another way can be in an autoclave type reactor, whose description of the process is found in Example 4.

[0013] The hydroprocessing (HDP) was performed in an autoclave type reactor as exemplified in Figure 1. The reactor was loaded with up to 15 g of catalyst and the ratio in grams DX / catalyst of 15/5, 15/10 and 15/15, keeping the amount of n-hexane constant, the type of zeolite and the type of metal. Before the reaction, the catalyst was reduced with a flow of H2 of 100 mL.min-1 from room temperature to 350 ° C with a heating rate of 10 ° C.min-1 and was maintained at this temperature for 240 min . The reaction was carried out between 1 and 24 h at 250 ° C and under 40 bar of H2 measured at 25 oC which under heating resulted in a final pressure of about 90 bar. At the end of the reaction, a pressure regulating valve followed by a device for gas measurement (when bypassing). This device measures the flow at atmospheric pressure through a bubble meter placed at the condenser outlet (5). DX was exploited between 10 and 20 g, keeping the amount of n-hexane constant (90 g). This mixture was introduced to the reactor (1) filled with an inert N2 atmosphere. The tests were performed with acetal mixed in n-hexane. Hydroprocessing (HDP) was also performed in a fixed bed reactor, as shown in Figure 2. In each test, the reactor (4) was loaded with 1g of catalyst. Before the reaction, the catalyst was reduced with a flow of H2 of 100 mL.min-1 from room temperature to 450 ° C with a heating rate of 10 ° C.min-1 and was maintained at this temperature for 60 min . The reaction was carried out for 2 h at 350 ° C and under 50 bar of H2, using a flow rate of 100 mL.min-1, the flow is measured at atmospheric pressure through a pressure regulating valve placed at the condenser outlet (5) .

[0014] A flow rate of DX (20% by weight) in n-hexane of 0.1 mL.min-1 was introduced into a container (1) filled with an inert atmosphere of N2 exerting a pressure of approximately 5 bar. Then, the charge was admitted directly to the reactor by means of an HPLC pump (2). The tests were performed with acetal mixed in n-hexane. The HDP of DX mixed with n-hexane will be demonstrated with examples:

Example 1

[0015] This example describes some bifunctional catalysts used to demonstrate how the process works. Catalysts were prepared containing a metallic function (pure palladium or mixed with copper) supported on HUSY, HY, HBEA and HZSM-5 zeolites, and their properties are described in Table 3.

Example 2

*entre parêntesis: seletividade de isômeros C6 em uma base de n-hexano.[0016] This example demonstrates the production of green hydrocarbons for use in gasoline, aviation kerosene and diesel. Catalysts containing copper and palladium (Cu-Pd / HBEA and Cu-Pd / ZSM-5) were used. In this example, the hydroprocessing was conducted in an autoclave type reactor (as shown in Figure 1) with a mechanical stirrer (2) using supported palladium catalysts from Example 1. In each test, the reactor (7) was loaded with 5 g of catalyst. Before the reaction, the catalyst was dried with N2 at a flow rate of 50 ml / min for 2 hours at 300 ° C, followed by a reduction for 2 hours with a flow rate of 50 ml / min of H2 at 300 ° C. Then, the reactor was cooled to 25 ° C to add the mixture of DX and n-hexane (5). A mixture consisting of 15 g of DX in 90 g of n-hexane converted in the presence of 15 g of catalyst was used as liquid filler. After adding the liquid charge, hydrogen (5) was added to a pressure of 40 bar of H2 measured at 25 oC. The temperature was increased to 250 ° C and after reaching that temperature it resulted in a final pressure of 90 bar. Both reactions were conducted for 24 h. The sum of the liquid, gaseous and coke fractions resulting from hydroprocessing showed values around 90%. The yields of compounds containing more than seven carbon atoms and comprising paraffins, naphthenics and less aromatic amounts were evaluated according to Table 4.

* in brackets: selectivity of C6 isomers on an n-hexane base.

[0017] The results described in Table 4 indicate that only in the presence of the mixture DX and n-hexane compounds containing more than seven carbon atoms were obtained. In addition, in the presence of Cu-Pd / HBEA compounds containing more carbon atoms were observed compared to the Cu-Pd / ZSM-5 catalyst. In both, the DX was completely converted.

[0018] The results of yield of products on carbon and hydrogen bases of DX (discounting the non-hexane not converted to the liquid phase) are shown in Table 5. A high percentage of carbon and hydrogen in the DX is observed in products of interest. In addition, there is an insignificant coke production in the presence of the two catalysts.

Example 3

[0019] This example demonstrates that the hydro-conversion can also be directed towards the production of more gas, that is, light products, by a simple change in the catalyst. The saturated hydrocarbons were obtained by hydroprocessing in an autoclave type reactor (as shown in Figure 1) and under similar conditions as in Example 2. The difference was only to use a mixture of 10g of DX in 90g of n-hexane and pure n-hexane (100g). The sum of liquid, gas and coke were above 90% for all tests according to Table 6.

[0020] In the presence of DX the gas fraction is substantially reduced. This effect is related to the severe suppression of the conversion of n-hexane that occurs due to the presence of DX as shown in Table 7. It is observed that the concentration of coke is negligible in all catalysts. Table 7 shows the conversion of DX and n-hexane and the selectivity of liquid products obtained in the hydroconversion of pure n-hexane and 10% DX / n-hexane during 24 hours of reaction in the presence of Pd / HZSM-5 and Pd / HBEA. For the two catalysts, the fraction containing five and fewer atoms (C5-) was the main one in the liquid phase. Demonstrating the role of catalysts to drive DX conversion.

[0021] An example of a chromatogram and specific products is described in Figure 3. In addition, the effect of removing copper on the products is shown in Figure 4 which indicates the two chromatograms of the tests with the catalysts Pd / HBEA and Cu-Pd / HBEA. A large increase in C5- products is visually noticed by the removal of copper.

Example 4

[0022] This example shows the effect of the ratio between DX and the catalyst. The catalytic test was performed in an autoclave reactor as described in Figure 1 and according to the conditions of Example 2 but exploring the DX / catalyst ratio. A mixture of 14.3% DX / n-hexane, that is, 15 g of DX and 90 g of n-hexane, was introduced into the reactor, and three mass loading / catalyst ratios were used: 3: 1, 1.5: 1 and 1: 1. The percentage of mass of liquid, gaseous and coke products resulting from the hydroprocessing of 14.3% DX / n-hexane using 5 g, 10 g and 15 g of Pd / HZSM-5 is shown in Table 8. In the same way as the previous examples the sum of the fractions is around 90%.

[0023] Table 8 indicates a pronounced decrease in coke, an increase in gas and a decrease in the liquid phase with an increase in the DX / catalyst ratio. The selectivity in liquid products resulting from the hydroconversion of 14.3% DX / n-hexane using Pd / HZSM-5 is shown in Table 9.

[0024] The test with 15 g of DX and 5 g of catalyst showed a low deoxygenation of the charge, confirmed by the high selectivity in oxygenated compounds, about 75%. With the increase in the amount of catalyst there was a better deoxygenation of the charge, reaching practically total deoxygenation in the test in which a charge / catalyst ratio of 1: 1 was used with a marked increase in the formation of the C7 + fraction. Comparing the 1.5 and 1 ratios, there is a slight increase in the amount of catalyst, a slight increase in the C5- fraction, an increase in the fraction of paraffins and C7 + naphthenes and a decrease in aromatics. Thus, the load / catalyst parameter can contribute to product distribution and optimize the conversion of acetal. We emphasize that the oxygenated fraction can be separated or even the reduction time can be extended to achieve a desired product composition.

Example 5

[0025] This example demonstrates that hydroconversion can also be carried out in another module: a fixed bed reactor with continuous flow of reagents instead of a batch reactor. So you can convert the reaction mixture in less time. Obtaining green hydrocarbon saturated by hydroprocessing in a fixed bed unit (as shown in Figure 2) using supported palladium catalysts from Example 1. The tests were carried out with the acetal mixed in n-hexane. In each test, the reactor (4) was loaded with 1 g of catalyst. Before the reaction, the catalyst was reduced with a flow of H2 of 100 mL.min-1 from room temperature to 450 ° C with a heating rate of 10 ° C.min-1 and was maintained at this temperature for 60 min . The reaction was carried out for 2 h at 350 ° C and under 50 bar of H2, using a flow rate of 100 mL.min-1, the flow is measured at atmospheric pressure through a pressure regulating valve placed at the condenser outlet (5) . A flow rate of DX (20% by weight) in n-hexane of 0.1 mL.min-1 was introduced into a container (1) filled with an inert N2 atmosphere exerting a pressure of approximately 5 bar. Then, the charge was admitted directly to the reactor by means of an HPLC pump (2).

[0026] For all tests, a test was also performed using pure n-hexane for comparison with the test of the mixture DX and n-hexane. The yield in products in the liquid and coke phase for the reactions is shown in Table 10, the gas was determined qualitatively.

[0027] The gas fraction is composed of CO, CO2 and hydrocarbons up to C5. However, this fraction has not been quantified. The amount of coke was greatly affected by the type of catalyst, particularly, lower coke concentrations were observed in the presence of zeolites ZSM-5 and BEA. The conversion of DX and n-hexane and the ratio of the products selected to the total products in the liquid phase (w / w%) and coke (w / w of the feed load) are shown in Table 11.

[0028] The conversion of the DX was complete in all tests. In the presence of DX, the conversion of n-hexane was significantly inhibited, decreasing up to 3 times. In the test with pure n-hexane, no products containing more than seven carbon atoms are observed. Therefore, n-hexane can be seen as a solvent for the reaction and as a carrier of acetals for the reactor. In addition, when comparing to Example 2, it is noted that under the conditions in which the batch process was carried out, less gas and coke are produced than the corresponding one in a fixed and more liquid bed, in addition it considerably increases the selectivity in products containing more than seven carbon atoms. Therefore, the conversion of DX to gas is maximized.

[0029] The selectivity in C7 + hydrocarbons is between 2.5 and 5%. Paraffins and naphthenes with 7 or more carbons (C7 +) and aromatic compounds were obtained only in the presence of the mixture of 20% DX in n-hexane. Therefore, mostly related to the presence of DX. These examples show the possibility of carrying out the process in a fixed bed reactor, however the catalysts formed too many light products. It should be noted that the coke formed is greatly influenced by the type of catalyst. Obviously, the oxygenated compounds can be removed or converted with a change in residence time and in the catalyst, as indicated in the following examples. In addition, two or more catalysts can be combined by physically mixing them. Thus, and optimizing the process conditions, it is also possible to control the fraction of saturated hydrocarbons in the kerosene band (C9-C16) and produce aviation biofuel in just one step.

Claims (9)

Process for obtaining green fuel from sugar acetals characterized by comprising the following steps:

• (a) Introduce a mixture of sugar and hydrocarbon acetals to a reactor containing a bifunctional catalyst (with an acidic and metallic function);
• (b) Submit the load to a hydrogen pressure greater than 5 bar and a temperature greater than 200 ˚C;
• (c) Recover the entire product containing more than seven carbon atoms and recycle the strip containing six carbon atoms or less to co-process with acetal or bio-petroleum.

Process, according to claim 1, characterized by occurring in a tubular reactor in the space time greater than 3 seconds, preferably in the range of 30-180 seconds. Process according to claim 1, characterized in that it takes place in a batch or batch reactor fed with residence time in the range 1 - 48h, preferably in the range between 5 - 24 hours. Process according to claim 1, characterized in that it uses a bifunctional catalyst containing an acid function of Brӧnsted or Lewis together with a metallic function such as, Ni, Co, Pt, Pd, Ir, Rh and Ru, pure or mixed with Cu metals , Fe, V, Ti and Zn. Process according to claim 1, characterized in that it uses a catalyst that can be previously reduced at a temperature above 200 ° C and dried before the reaction. Process according to claim 1, characterized in that the batch reactor uses an acetal / catalyst ratio of less than 3, preferably in the range of 0.5 to 1.5. Process according to claim 1, characterized by producing a mixture of green hydrocarbons with different compositions with the following functionalities: aromatics, alkyl naphthenics and paraffins. Process according to claim 1, characterized by producing bio-hydrocarbons that can be used directly as fuel or mixed with conventional hydrocarbon streams to produce the final fuel for application such as gasoline, aviation kerosene and diesel. Process according to claim 1, characterized in that the acid catalyst is obtained by recycling the catalyst after use, removing the coke deposit by the regeneration process such as calcination in the oxidizing environment and hydrothermal treatment.

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