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    • 专利摘要:
    Production of fuels from biomass and heavy naphtha. The present invention relates to a process for the production of a liquid fuel with a high content of alkylcyclohexanes and low in oxygenated compounds comprising at least: A first alkylation step of an alkylbenzene, preferably mono, di, tri, or tetrasubstituted with at least one furanic alcohol with formula 1 in the presence of at least one heterogeneous acid catalyst {image-01} Where r1 is h, hydroxymethyl, formyl, acetyl or an aliphatic or aromatic or heteroaromatic moiety R2 is h or an aliphatic or aromatic or heteroaromatic moiety R3 is h or an aliphatic or aromatic or heteroaromatic moiety - a second step of hydrogenation and catalytic dehydration of the compound obtained in the first step, a), in the presence of hydrogen, using suitable hydrogenation and dehydration catalysts. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2557393A2
    申请号:ES201430950
    申请日:2014-06-23
    公开日:2016-01-25
    发明作者:Avelino Corma Canós；Sara Iborra Chornet；Maria José CLIMENT OLMEDO；Karen Sulay ARIAS CARRASCAL
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    5 Field of the invention
    This invention belongs to the field of the transformation of vegetable biomass into transport fuels. 10 Background of the Invention
    Biofuels or biofuels are fuels from biomass (mainly vegetable), with similar characteristics to fossil fuels. This allows its use in barely modified engines with important environmental advantages15. In the event that the biofuels are of vegetable origin, the carbon dioxide balance in its combustion is neutral since it can be considered that the same amount of carbon dioxide produced in said combustion has previously been consumed from the carbon from the atmosphere through the photosynthesis cycles (over a period of years). In addition, biofuels do not contain nitrogen compounds or
    20 sulfur Therefore, in their combustion the oxides of these elements, mainly responsible for photochemical smog and acid rain, are not produced.
    Biodiesel (or FAMEs), consisting of methyl and ethyl esters of fatty acids (together with bioethanol) was the first generation of biofuels for transport. 25 However, biodiesel has some disadvantages, such as the need to adapt diesel engines to be able to use 100% biodiesel as fuel. At present, these adaptations can be made technically, but in order to avoid the economic expense that a complete change would entail, only biodiesel up to 5% is added to conventional diesel. Another drawback of biodiesel is that improper storage 30 can favor its decomposition and release fatty acids that can cause problems in ducts and filters, in addition to possible corrosion caused by its acidic properties. However, the main reason why biodiesel cannot replace conventional diesel in the future is the origin of the former. Vegetable oil is mainly obtained from crop plants which makes it compete for arable surface. This means that in the end biodiesel production competes with the




    food production, increasing the price of some staple foods considerably.
    To avoid competition with food production, the
    5 biofuels called second generation, which should avoid the use of any plant biomass that requires arable land. On these bases it is intended to develop second generation biofuels from cellulose or hemicellulose that can come from wood (shavings or sawdust) but also from any type of plant biomass residue.
    10 Recently, possible solutions to the problem of the production of second generation biofuels have been described. For example in the process described by J. A. Dumesic et al. (Science 2005, 308, 1446–1450; PTC Int. Appl. WO2008151178, 2008; US Patent 20090124839, 2007) the aldol condensation of 5
    15 hydroxymethylfurfural (HMF) or furfural with acetone (as a connector of two furanic molecules) to obtain molecules with 9, 12 or 15 carbon atoms that in subsequent steps can be hydrogenated to their corresponding alkanes. However, a cross-aldol condensation implies, by its nature, low selectivity, since acetone can condense with itself. To increase selectivity the
    Condensation is carried out in an aqueous phase, and hydrogenation in hexadecane as a solvent at 120 ° C which implies a process increase (Appl. Catal. B Environ. 2006, 66, 111-118).
    An alternative solution for the production of second generation biofuels is
    25 described in R. D. Cortright, WO2008109877, 2007; Int. Sugar J. 2008, 110, 672-679, producing in a first step mixtures of compounds with 4 carbon atoms or more from oxygenated compounds in an aqueous solution in the presence of a deoxygenation catalyst and a condensation catalyst (Aqueous Phase Reforming). In order to obtain high levels of alkanes, the inventors use basic catalysts to condense
    30 ketones and aldehydes as in the case of Dumesic or the oligomerization of alkenes. However, the way they combine molecules with low carbon numbers is not enough to get molecules with a sufficient number of carbon atoms to be used as diesel. Thus, the content in raw products of molecules with ten carbon atoms or greater is less than 50%.




    Dumesic in Angew. Chem. Int. Ed. 2007, 46, 7164-7183, describes other processes such as dehydration and hydrogenation of sorbitol or xylitol to light linear alkanes. However, this last process cannot be considered as an alternative to produce hydrocarbons that increases the number of carbon atoms to a greater number of
    5 five or six initials (see also Angew. Chem. Int. Ed. 2004, 43, 1549–1551).
    More recently, in WO 2011/070210 A. Corma et al. describe a process for the production of a liquid fuel of 11 carbons and more consisting of a first step of alkylation of 2-methylfuran (Sylvan) with a furanic alcohol 10 produced in situ by hydroxyalkylating 2-methylfuran with carbonyl compounds to give compounds of structure 2- (furanylmethyl) -5-methylfuran. These compounds are catalytically hydrogenated / dehydrated in a second step, to give open structure alkanes that may contain one or more branches and that depending on the number of carbons can be used as diesel fuel or high quality kerosene. The same authors present in WO2011 / 157876 a process for the production of a liquid fuel with a high alkane content comprising in a first step the treatment of 2-methylfuran with an acid catalyst and water to form a mixture of products with at least ten carbon atoms and a second step of hydrogenation and catalytic dehydration of the product or the
    The mixture obtained in the first step, using suitable hydrogenation and dehydration catalysts, giving rise to open structure alkanes with one or more branches.
    Another strategy to obtain precursor molecules of diesel fuel or kerosene to
    Starting from biomass-derived furan compounds such as 5-hydroxymethylfurfural (HMF) is the Friedel-Crafts alkylation of sands with HMF. For example Lovel et al. (Angew. Chem. Int. Ed., 2005, 44, 3913) describes the alkylation of o-xylene with HMF using FeCl3 as Lewis acid catalyst at 80 oC obtaining 37% of a mixture of substituted xylenes after 24h reaction . More recently, Zhou et al.
    30 (ChemSusChem, 2013, 6, 383) describes the alkylation of Friedel-Crafts of mesitylene with HMF using nitromethane as solvent. When FeCl3 is used as a catalyst, mesitylfurfural is obtained in a 94% yield, while when using ptoluenesulfonic acid only 76% is obtained. Additionally, the authors describe that formic acid acting as solvent and catalyst can be used to carry out a
    35 cascade process starting from fructose that involves dehydration of fructose in



    HMF followed by alkylation of mesitylene, however the yields to mesitylfurfural are modest (20-70%).
    However, these methods have important problems such as the use of
    5 volatile and toxic solvents such as nitromethane and the use of homogeneous acid catalysts that require a neutralization step with the consequent generation of waste and the impossibility of recovering and reusing the acid catalyst. Therefore it is desirable to develop new sustainable catalytic processes, which involve the use of heterogeneous, stable and reusable catalysts to carry out this
    10 type of alkylations in the absence of solvents.
    In the present invention a process is presented to transform products derived from biomass (furanic alcohols) in combination with alkylbenzene compounds derived from heavy naphtha into liquid fuels in the range of
    15 kerosene and diesel of good quality. The invention involves the use of micro and mesoporous aluminosilicates for the first time as highly selective heterogeneous acid catalysts for carrying out Friedel-Crafts alkylation of furyl alcohols with sands, followed by catalytic hydrogenation of the alkylated product to obtain saturated hydrocarbons. Description of the invention
    The present invention relates to a process for the production of a liquid fuel with a high content of alkylcyclohexanes and low in oxygenated compounds comprising at least: Ͳ A first alkylation step of an alkylbenzene, preferably mono, di, tri,
    or tetrasubstituted with at least one fury alcohol with formula 1 in the presence of at least one heterogeneous acid catalyst
    30




    Where R1 is H, hydroxymethyl, formyl, acetyl or an aliphatic or aromatic or heteroaromatic moiety R2 is H or an aliphatic or aromatic or heteroaromatic moiety R3 is H or an aliphatic or aromatic or heteroaromatic moiety
    5Ͳ A second step of hydrogenation and catalytic dehydration of the compound obtained in the first step, a), in the presence of hydrogen, using suitable hydrogenation and dehydration catalysts.
    According to a preferred embodiment, the alkyl benzene compound may be a benzene.
    10 mono, di, tri, or tetrasubstituted with linear or branched alcanic chains between 1 and 3 carbons.
    According to the process of the present invention, the alkylbenzene compound may preferably be selected from monosubstituted benzenes, any regioisomer of
    15 disubstituted, trisubstituted, tetrasubstituted benzenes with linear or branched alcanic chains between 1 and 3 carbons and combinations thereof. The alkylbenzenes used in the process are readily available, for example, from the fraction of heavy naphtha that is obtained in the reforming process.
    According to a particular embodiment, the alkylbenzene compound may be a mono substituted benzene selected from toluene, ethylbenzene, propylbenzene, isopropylbenzene and combinations thereof.
    According to another particular embodiment, the alkylbenzene compound can be any
    Regioisomer of benzenes disubstituted with linear or branched alkanic chains between 1 and 3 carbons selected AS FOR EXAMPLE from o-, m- and para-xylenes, o-, m- and pethyl, isopropyl or p-n-propyl toluene and combinations thereof.
    According to another particular embodiment, the alkylbenzene compound can be any
    30 benzene regioisomer trisubstituted with linear or branched alcanic chains between 1 and 3 carbons selected from 1,2,3, -trimethylbenzene, 1,2,4, -trimethylbenzene, 1,2, -dimethyl-3-ethylbenzene, 1,4-dimethyl -2-ethylbenzene and combinations thereof.
    According to another particular embodiment, the alkylbenzene compound can be any regioisomer of tetrasubstituted benzenes with linear or branched alcanic chains



    between 1 and 3 carbons, such as 1,2,4,5-tetramethylbenzene and combinations thereof.
    According to the present invention, the furanic alcohol 1 is preferably selected from
    5 5-hydroxymethyl furfural, furfuryl alcohol, 5-methylfurfuryl alcohol, 2,5-di (hydroxymethyl) furan, 5acetyl-2-fufuryl alcohol, alpha-methyl-2-furanmethanol, alpha, 5-dimethyl-2-funmethanol, alpha, ethyl-5-methyl-2-furanmethanol, 5-methyl-alpha-propyl-2-furanmethanol and combinations thereof.
    According to the present invention, the mixture of alkylcyclohexanes of the product can be
    10 modify by varying the reagents used. The first step of the process consists in the alkylation of an alkylbenzene with a derivative of furufuryl alcohol (compound 1), obtaining molecules with at least 12 carbon atoms connected.
    Preferably, the product obtained in step 1 can have a structure of 15 benzylfuran, preferably 5-benzylfuran (2)
    Where R1 is H, hydroxymethyl, formyl, acetyl or an aliphatic or aromatic or heteroaromatic moiety.
    R2 is H or an aliphatic or aromatic or heteroaromatic moiety R3 is H or an aliphatic or aromatic or heteroaromatic moiety Where the benzyl ring of the benzyl group may be mono, di, tri or tetrasubstituted in any position with linear or branched alcanic chains between 1 and 3 carbons.
    The second step of the process of the present invention is the hydrogenation / dehydration of the product (2) obtained to give di, tri, tetra or penta alkylcyclohexanes with alkanic chains between 1 and 10 carbon atoms that may contain one or more branches. To achieve a narrow range in the number of 30 carbon atoms of the final product, it is important that the process be highly selective




    in both steps, but particularly in the first step since polyalkylations can occur on the benzene ring or the polymerization of the hydroxyalkylfuran.
    Thus, for example, the alkylation of toluene with 5-hydroxymethylfurfural results in a molecule 5 with thirteen carbon atoms which, after hydrogenation / dehydration, gives rise to a mixture of alkyl cyclohexane isomers with structure:
    The hydroxyalkylfurans can come from furanic derivatives obtained by dehydrating pentoses (for example furfural) or hexoses (5-hydroxymethylfurfural). So
    For example, furfuryl alcohol can be obtained by hydrogenation of furfural or 5-methyl furfuryl alcohol from the hydrogenation of 5-methylfurfural which in turn can also be obtained from biomass by a hydrogenation process. (Angew.Chem.Int.Ed., 2008, 47, 7924).
    According to a preferred embodiment, the alkylation of the first step is carried out using at least one heterogeneous acid catalyst selected from microporous aluminosilicate preferably selected from USY zeolite with Si / Al ratio between 2.5 and 27, Beta zeolite with Si / Al ratio between 12 and 50, ITQ-2 zeolite with Si / Al ratio between 12 and 50 and Mordenite zeolite with Si / Al ratio between 5 and 25 and mesoporous aluminosilicates such as MCM-41
    20 with Si / Al ratio between 12 and 50.
    According to a preferred embodiment, the alkylation of the first step can be carried out at a temperature between 50 and 170 oC and during a contact time between 15 min and 24 hours, more preferably between 80 and 150 oC and during a contact time between 1 hour and 15
    25 hours
    According to another preferred embodiment, the alkylation of the first step can be carried out using between 5 and 30% by weight of heterogeneous catalyst with respect to the fury alcohol (1), while the molar concentration of the fury alcohol (1) in the
    The alkylbenzene is comprised, preferably between 0.5 and 0.05M, being able to be carried out in a reactor selected from a discontinuous stirred tank type reactor or a continuous fixed bed reactor.




    According to a particular embodiment, the hydrogenation / dehydration of the second step can be carried out at a temperature between 150 oC and 450 oC, preferably between 200 and 400 oC and at a pressure between 0.1 bar and 70 bar and preferably between 2 bar and 50 bar .
    5 According to a preferred embodiment the catalyst of the second step may comprise at least one metal function and one dehydrating function. Preferably, the catalyst may comprise at least one of the elements selected from Ni, Pd, Pt, Re, Rh, Ru, Cu, all of which are supported, as well as combinations thereof, the support being preferably selected from active carbon, a inorganic oxide selected
    10 preferably between alumina, zirconia, titania, silica and combinations thereof.
    This second step of the process of the present invention can be carried out using a reactor selected between a stirred tank type discontinuous reactor and a fixed bed continuous reactor.
    An advantage of the present invention is its flexibility with respect to the final product obtained, its choice being possible according to the use to be given. Depending on the choice of reagents, the fuel obtained in the alkylation / hydrogenation / dehydration reaction can be used as kerosene, as diesel or
    20 allocate it to other fractions. The method allows to obtain mixtures of alkylcyclohexanes with high content of molecules of 12 and more carbons.
    Another advantage of the present invention is its flexibility with respect to the raw material since it is possible to use biomass from different sources such as that obtained from
    25 pentoses and hexoses. An additional advantage of the present process from the economic and ecological point of view is that no solvent is needed for its realization and the only by-product that is formed in the alkylation / hydrogenation / dehydration process is water.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, component additives or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples are provided by way of illustration, and are not intended to be
    Limitations of the present invention.




    Examples Example 1: Synthesis of ITQ-2 material
    The pure silica laminar precursor (MWW type) was prepared from a gel of composition:
    5 SiO2: 0.25 TMAdaOH: 0.3HMI: 0.1NaCl: 44H2O, where HMI is hexamethyleneimine and TMAdaOH is trimethylammonium hydroxide. The methodology used is widely described in the literature [Corma, A., Fornés, V., Perguer, S. B., Maesen, Th. L. M., Buglass, J. G., Nature, 1998, 396, 353.].
    10 The preparation of the ITQ-2 delaminated material from the sheet precursor comprised several steps: swelling, dispersion, flocculation and calcination. To 10 g of the laminar precursor dispersed in 40 g of water were added 200 g of solution of cetyltrimethylammonium hydroxide (CTAOH, Sol. 29% in water) and 50 g of tetrapropylammonium hydroxide (TPAOH, Sol. 50% in water), reaching the final pH at a value of 12.5. The mixture was heated
    15 to 50 oC for 16 hours to facilitate swelling of the sheets of the material. Then, the suspension was subjected to an ultrasonic treatment for 1 hour, to disperse the sheets, and the pH was lowered to 3.0 by the addition of HCl facilitating flocculation of the delaminated solid. The latter was recovered by centrifugation, washed with water, dried at 60 oC for 12 hours, and calcined at 540 oC for 3 hours in N2 and then for 6 hours
    20 in air.
    From the laminar precursor of the MWW zeolite, the delaminated ITQ-2 zeolite is prepared. The ITQ-2 delaminated material (SBET • 700 m2 / g) contains individual sheets of §2.5 nm thick that have a hexagonal distribution of “cups” located on both sides of
    25 each sheet.
    These cups, delimited by a ring of 12 members (12MR) and with an opening of 0.7 x
    0.7 nm approximately, are connected to the cups on the other side of the
    sheet by a ring of 6MR, while a system of sinusoidal channels of 10MR runs around the cups inside each sheet.
    Example 2: Synthesis of 5- (o-, m- and p-methyl) becilfuran-2-carbaldehyde with heterogeneous acid catalysts
    To a 50-ml two-mouth flask connected to a refrigerant and submerged
    35 in a thermostated silicone bath, HMF (0.5 mmol) and toluene (25 ml) were added. The mixture was heated at 115 ° C under magnetic stirring and under a nitrogen atmosphere. TO




    Then 15.75 mg (25% by weight with respect to HMF) of the heterogeneous catalyst was added. The catalyst before use was activated, heating it at 200 oC and under reduced pressure (2 torr) for 2 hours, in order to remove adsorbed water. During the course of the reaction samples were taken periodically, which were analyzed by gas chromatography (GC) using nonane as an external standard. The gas chromatograph used was equipped with a flame ionization detector (FID) and a capillary column (HP5, 30 m x 0.25 mm x 0.25mm). At the end of the reaction, the catalyst was separated from the organic phase by filtration, and in all cases the molar balance was greater than 95%. The analysis of the organic phase using the Gas-Mass Chromatography (CG) techniques
    10 MS) and Nuclear Magnetic Resonance Spectroscopy (1H-NMR and 13C-NMR-C) that allowed to determine the composition of the mixture. The only byproduct detected was 5.5 '(oxy-bis (methylene)) - bis-2-furfural (OBMF).
    5- (o- m and p-Methyl) benzylfuran-2-carbaldehyde: 1H NMR (CDCl3): į 9.53 (s, 2H), 7.11–7.32
    15 (m, 8H), 6.16 (d, J = 2.8 Hz, 1H), 6.12 (d, J = 2.5 Hz, 1H), 4.08 (s, 1H), 4.02 (s, 1H), 2.34 (s, 3H ), 2.28 (s, 3H); 13C NMR (CDCl3): į 177.7, 177.2, 162.4, 161.8, 157.2, 152.17, 148.9, 136.7, 134.4, 130.6, 129.8, 129.6, 129.5, 128.8, 128.7, 128.5, 127.8, 127.4, 126.4, 125.9, 123.1, 121.8 , 111.8, 109.9, 109.7, 109.6, 34.8, 34.5, 32.7, 21.3, 21, 19.4. CG-MS: m / z 200, 185, 171, 128, 115, 91, 77.
    5.5 '- (oxy-bis (methylene)) - bis-2-furfural (OBMF): 1H NMR (300 MHz, CDCl3): į 9.64 (s, 2H, 2 × CHO), 7.22 (d, J = 3.5 Hz, 2H, 2 × C3-H), 6.54 (d, J = 3.6 Hz, 2H, 2 × C4-H), 4.64 (s, 4H, 2 × CH2). CG-MS: m / z 234 (C12H10O5) 3%, 206 (31%), 125 (10%), 110 (46%), 109 (100%), 81 (61%), 53 (31%).




    Table 1 shows the results of some of the heterogeneous acid catalysts used:
    Table 1
    Yield Yield (%) Conv. Sel (%) Catalyst Yes / Al (%) 5
    (%) 5-RentedOBMF Rented
    USY 15 100 5 95 95 HBeta 12.5 69 15 54 78 ITQ-2 15 99 1 99 99 MCM-41 12 99 15 84 85
    Example 3: Influence of the molar concentration of HMF on the synthesis of 5- (o-, m-pmethyl) becilfuran-2-carbaldehyde
    The alkylation of toluene with HMF was carried out with several experiments, varying in each case the volume of toluene. Thus, an experiment consisted of adding to a flask that
    10 contained 0.5 mmol HMF and 2.5 ml of toluene (0.2 mol L-1 molar concentration) at the temperature of 115 oC, the ITQ-2 zeolite catalyst (Si / Al 15) (25% by weight with respect to the HMF) previously activated, as described in example 1. The results using different molar concentrations of HMF are shown in Table 2.
    15 Table 2
    Conc. Molar Rto. (%) Rto. (%) Selectivity Tol (ml) Time (h) (mol / L) rented OBMF rented
    2 61 29 66
    0.2 2.5
    8 68 28 69 2 70 21 77
    0.1 5
    8 83 17 83 2 79 18 81
    0.1a 5 8 87 13 87 2 85 15 85 0.1b 5 8 96 4 96 2 74 14 84
    0.05 10
    8 80 15 82




    2 89 2 98
    0.02 25
    8 98 1 99
    Reaction conditions: HMF (0.5 mmol), ITQ-2 (15) (15.75 mg), 115 oC, N2, 30% by weight ITQ-2 (15) with respect to HMF; b 50% by weight of ITQ-2 (15) compared to HMF
    Example 4: Variation of the conditions of Example 3.
    5 The alkylation of toluene with HMF was carried out according to example 3 but at a temperature of 150 ° C. Thus, an experiment consisted of adding to a flask containing
    0.5 mmol of HMF and 2.5 ml of toluene (Molar concentration = 0.2M) at the temperature of 150 oC, the ITQ-2 zeolite (Si / Al 15) (25% by weight with respect to the HMF) previously activated, as described in Example 1. Results using different concentrations
    10 HMF / Toluene molars are shown in Table 3:
    Table 3
    Molar Conc. (Mol / L) Tol (ml)Time (h)Rto. (%) rentedRto. (%) OBMFRented selectivity
    0.2 2.52 870 8322 1476 85
    0.1 52 885 9611 489 96
    Reaction conditions: HMF (0.5 mmol), ITQ-2 (15) 25% by weight of ITQ-2 (15) with respect to HMF at 150 oC, N2
    Example 5: Alkylation of a mixture of aromatic hydrocarbons of similar composition to a heavy fraction of reforming with 5-Hydroxymethylfurfural Alkylation with HMF has been carried out with a mixture of composition similar to a heavy fraction from the reforming process, which consists of a mixture of
    20 1,2,3-trimethylbenzene (54 v / v%), 3-ethyltoluene (33.4 v / v%), n-propylbenzene (6 v / v%) and oxylene (6.6 v / v%). The alkylation was carried out in a closed reactor following the procedure described in Example 1. Thus a solution of 5-hydroxymethylfurfural (0.5 mmol, 63 mg) and 5 ml of the aromatic mixture at 150 oC was added 15.75 mg of ITQ-2 (Yes / Al 15). Crude oil analysis after 6.5 h of reaction indicated that the total yield
    25 of products rented with HMF was 90% with a selectivity of 93% - Majority alkylation products corresponded to the most activated aromatic hydrocarbons, for example o-xylene (Rto. 41% rented) and 1,2,3 -trimethylbenzene (Rto. 37% of alkylated).




    Example 6: Hydrogenation / dehydration of 5- (o-, m-p-methyl) benzylfuran-2 carbaldehyde
    The mixture of 5- (o-, m-p-methyl) becilfuran-2-carbaldehyde isomers (10.01 g) prepared according to Example 1, was introduced into a tubular shaped stainless steel reactor. The 5 dimensions of the reactor were 0.77 cm internal diameter and 38 cm long. The reactor initially contained 6,675 g of a mixture of Pt / C (80% by weight) and Pt / TiO2 (20% by weight) and in the final part 3 grams of silicon carbide as a catalyst bed. The mixture was injected at a rate of 0.1 ml / min and at a temperature of 65 oC that increased to 350 oC. At all times the hydrogen pressure was maintained at 40 bars. After 1.67 h of reaction,
    10 88% by weight of a liquid mixture was obtained consisting of an aqueous phase (15% by weight) and an organic phase (85% by weight). The organic phase was analyzed by two-dimensional gas chromatography (Varian 3800 CG, equipped with two detectors (TCD) and one (FID)). Table 4 below shows the results obtained in terms of composition and in the Tables 5 and 6 some of the properties of the fuel
      Table 4 Saturated (%) Compounds 77.49
    C13 naphthenes 37.58 C12 naphthenes 0.76 Polinaphthenes 10.44 n-hexane 2.48 C7 naphthenes 13.92 Other saturated 12.30 mono-aromatic 16.82
    Toluene C7 6.31 Mono-aromatic C13 8.83 Mono-aromatic C12 0.26 Other aromatic 2.61
    di-aromatic 2.70
    tri-aromatic 1.59
    Polar 0.21
    Total 100.00




    Table 5. Boiling Temperature Distribution (% by weight)
    Percentage (%) T (oC)
    0.5 68.73 10 104.89 20 110.62 30 216.28 40 216.28 50 216.28 60 232.78 70 235.40 80 235.40 90 268.17 99.5 285.00
    5 Table 6. Fuel characteristics
    RON 93.21
    MON 87.95
    Temperature @ V / L = 20 (oC) 108.92


    权利要求:
    Claims (23)
    [1]
    1. A process for the production of a fuel characterized in that it comprises at least:
    5 a) A first alkylation step of at least one alkylbenzene substituted with at least one furanic alcohol with formula 1 in the presence of at least one heterogeneous acid catalyst
    Where R1 is H, hydroxymethyl, formyl, acetyl or an aliphatic or aromatic or heteroaromatic moiety R2 is H or an aliphatic or aromatic or heteroaromatic moiety R3 H or an aliphatic or aromatic or heteroaromatic moiety b) A second step of catalytic hydrogenation and dehydration of the compound
    15 obtained in a).
    [2]
    2. A process according to claim 1, characterized in that the alkylbenzene is mono, di, tri or tetrasubstituted with linear or branched alkaline chains between 1 and 3 carbons.
    [3]
    3. A process according to claim 2, characterized in that the alkylbenzene is selected from monosubstituted benzenes, any regioisomer of disubstituted, trisubstituted and tetrasubstituted benzenes with linear or branched alkanic chains between 1 and 3 carbons and combinations thereof.
    [4]
    4. A process according to claim 3, characterized in that the alkylbenzene compound is a mono substituted benzene selected from toluene, ethylbenzene, propylbenzene, isopropylbenzene and combinations thereof.
    A method according to claim 3, characterized in that the alkylbenzene compound is a disubstituted benzene regioisomer selected from o-, m- and paraxylenes, o-, m- and p-ethyl, p-isopropyl or pn-propyl toluene and combinations thereof.


    [6]
    6. A process according to claim 3, characterized in that the alkylbenzene compound is a trisubstituted benzene regioisomer selected from 1,2,3, trimethylbenzene, 1,2,4, -trimethylbenzene, 1,2, -dimethyl-3-ethylbenzene, 1,4-dimethyl-2-ethylbenzene and combinations thereof.
    [7]
    7. A process according to claim 3, characterized in that the alkylbenzene compound is a tetrasubstituted benzene regioisomer selected from 1,2,4,5 tetramethylbenzene and combinations thereof.
    A method according to claim 1, characterized in that the fury alcohol 1 is selected from 5-hydroxymethyl furfural, furfuryl alcohol, 5-methylfurfuryl alcohol, 2,5di (hydroxymethyl) furan, 5-acetyl-2-furfuryl alcohol, alpha methyl-2-furanmethanol, alpha, 5-dimethyl-2furanmethanol, alpha, ethyl-5-methyl-2-furanmethanol and 5-methyl-alpha-propyl-2-furanmethanol and combinations thereof.
    [9]
    9. A process according to claim 1, characterized in that the product obtained in the first step has the 5-benzylfuran structure of formula 2
    Where R1 is H, hydroxymethyl, formyl, acetyl or an aliphatic or aromatic or heteroaromatic moiety. R2 is H or an aliphatic or aromatic or heteroaromatic moiety R3 H or an aliphatic or aromatic or heteroaromatic moiety Where the benzyl ring of the benzyl group may be mono, di, tri or
    25 tetrasubstitute in any position with linear or branched alcanic chains between 1 and 3 carbons.
    [10]
    10. A process according to claim 1, characterized in that the acid catalyst
    used in the first step is a heterogeneous catalyst selected from microporous aluminosilicate (zeolites), mesoporous aluminosilicate and combinations thereof.


    [11]
    11. A process according to claim 10, characterized in that the catalyst is a USY zeolite with Si / Al ratio between 2.5 and 27.
    [12]
    12. A process according to claim 10, characterized in that the catalyst is a Beta zeolite with a Si / Al ratio between 12 and 50.
    [13]
    13. A process according to claim 10, characterized in that the catalyst is an ITQ-2 delaminated zeolite with Si / Al ratio between 12 and 50.
    [ 14]
     14. A process according to claim 10, characterized in that the catalyst is a mordenite zeolite with Si / Al ratio between 5 and 25.
    [15]
    15. A process according to claim 10, characterized in that the catalyst is an MCM-41 mesoporous aluminosilicate with Si / Al ratio between 12 and 50.

    [16]
    16. A process according to claim 1, characterized in that the alkylation of the first step is carried out at a temperature between 50 and 170 oC and during a contact time between 15 min and 24 hours.
    [ 17]
     17. A method according to claim 16, characterized in that the alkylation of the first step is carried out at a temperature between 80 and 150 oC and during a contact time between 1 hour and 15 hours.
    [18]
    18. A method according to claim 1, characterized in that the alkylation of the
     First step is carried out using between 5 and 30% by weight of heterogeneous catalyst with respect to the fury alcohol.
    [19]
    19. A process according to claim 1, characterized in that the alkylation of the
    First step is carried out using a molar concentration of the fury alcohol in the alkylbenzene between 0.5 and 0.05 M.
    [20]
    20. A method according to claim 1, characterized in that the alkylation of the first step is carried out using a reactor selected between a stirred tank-type discontinuous reactor and a fixed bed continuous reactor.


    [21]
    21. A process according to claim 1, characterized in that the hydrogenation / dehydration of the second step is carried out at a temperature between 150 oC and 450 oC.
    22. A process according to claim 1, characterized in that the hydrogenation of the second step is carried out at a hydrogen pressure between 0.1 bar and 70 bar.
    [23]
    23. A process according to claim 1, characterized in that the catalyst of the second step comprises at least one metal function and one dehydrating function.
    [24]
    24. A method according to claim 23, characterized in that the catalyst of the second step comprises at least one element selected from Ni, Pd, Pt, Re, Rh, Ru, Cu, supported and combinations thereof.
    A method according to claim 24, characterized in that the support is selected from active carbon, an inorganic oxide and combinations thereof.
    [26]
    26. A method according to claim 25, characterized in that the support is a
    inorganic oxide selected from alumina, zirconia, titania, silica and combinations thereof.
    [27]
    27. A method according to claim 1, characterized in that the hydrogenation / dehydration of the second step is carried out using a reactor selected between a stirred tank-type discontinuous reactor and a continuous bed reactor
    25 fixed.
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    同族专利:
    公开号 | 公开日
    ES2557393R2|2016-04-19|
    WO2015197899A1|2015-12-30|
    ES2557393B1|2017-01-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US7880049B2|2006-06-06|2011-02-01|Wisconsin Alumni Research Foundation|Production of liquid alkanes in the jet fuel range from biomass-derived carbohydrates|
    ES2362248B1|2009-12-11|2012-05-10|Universidad Politecnica De Valencia|LIQUID FUEL PRODUCTION FROM 2-METHYLFURAN.|CN110437182B|2019-07-16|2021-07-20|南昌大学|Method for synthesizing bismethane BMFM from 5-methylfurfuryl alcohol 5-MFA|
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201430950A|ES2557393B1|2014-06-23|2014-06-23|PRODUCTION OF FUELS FROM BIOMASS AND HEAVY NAFTA|ES201430950A| ES2557393B1|2014-06-23|2014-06-23|PRODUCTION OF FUELS FROM BIOMASS AND HEAVY NAFTA|
    PCT/ES2015/070481| WO2015197899A1|2014-06-23|2015-06-22|Production of fuels from heavy naphtha and biomass|
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