Hydrocarbon composition useful as a fuel and fuel oil containing a petroleum component and a component of a biological origin

Abstract

The invention relates to a hydrocarbon composition, which can be used as a fuel and/or fuel oil, containing a petroleum component (A) and a component of a biological origin (B), wherein the component of a biological origin is present in a quantity of up to 75% by volume with respect to the total composition. Said component of a biological origin (B) is prepared starting from a mix of a biological origin (C) containing esters of fatty acids, with possible aliquots of free fatty acids, by means of a process which comprises the following steps: 1) hydrodeoxygenation of the mix of a biological origin; 2) hydroisomerization of the mix resulting from step (1), after possible water and gas flow separation, wherein said hydroisomerization is preferably carried out in the presence of a catalytic system comprising: a) a carrier of an acidic nature, comprising a completely amorphous micro-mesoporous silica-alumina, with a SiO 2 /Al 2 O 3 molar ratio ranging from 30 to 500, a surface area larger than 500 m2/g, a pore volume ranging from 0.3 to 1.3 ml/g, an average pore diameter smaller than 40 A, b) a metal component containing one or more metals of group VIII, possibly mixed with one or more metals of group VIB.

1 ) A hydrocarbon composition, containing a petroleum component (A) and a component of a biological origin (B), wherein said component (B) is present in a quantity of up to 75% by volume with respect the total composition, and wherein said component (B) is prepared starting from a mixture of a biological origin (C) containing esters of fatty acids, with possible aliquots of free fatty acids, by means of a process comprising the following steps:
 1) hydrodeoxygenation of the mixture of a biological origin (C);   2) hydroisomerization of the mixture resulting from step (1), after possible water and gas flow separation.   
     
     
         2 ) The composition according to  claim 1 , containing a petroleum component (A) and a component of a biological origin (B), wherein said component (B) is present in a quantity of up to 75% by volume with respect the total composition, and wherein said component (B) is prepared starting from a mixture of a biological origin (C) containing esters of fatty acids, with possible aliquots of free fatty acids, by means of a process including the following steps:
 1) hydrodeoxygenation of the mixture of a biological origin (C);   2) hydroisomerization of the mixture resulting from step (1), after possible water and gas flow separation, said hydroisomerization being effected in the presence of a catalytic system comprising:
 a. a carrier of an acidic nature, comprising a completely amorphous micro-mesoporous silica-alumina, with a SiO 2 /Al 2 O 3  molar ratio ranging from 30 to 500, a surface area greater than 500 m 2 /g, a pore volume ranging from 0.3 to 1.3 ml/g, an average pore diameter smaller than 40 Å, 
 b. a metal component containing one or more metals of group VIII, possibly mixed with one or more metals of group VIB. 
   
     
     
         3 ) The composition according to  claim 1  or  2 , wherein component (B) is present in a quantity of up to 40% by volume with respect to the total composition. 
     
     
         4 ) The composition according to  claim 1  or  2 , wherein the petroleum component (A) is a diesel cut or a blend of diesel cuts. 
     
     
         5 ) The composition according to  claim 4 , wherein the diesel cut is selected from medium distillates. 
     
     
         6 ) The composition according to  claim 5 , wherein the diesel cut is selected from distillates having a boiling point ranging from 180 to 380° C. 
     
     
         7 ) The composition according to  claim 4 ,  5  or  6 , wherein the cuts are selected from gas oils from primary distillation, gas oils from vacuum distillation and from thermal or catalytic cracking, fuels coming from Fischer-Tropsch processes, fuels of a synthetic origin and mixtures thereof. 
     
     
         8 ) The composition according to  claim 7 , wherein the diesel cut is a desulphurized gas oil coming from fluid bed catalytic cracking (LCO). 
     
     
         9 ) The composition according to one or more of the previous claims, wherein the petroleum component (A) is a hydrogenated diesel cut or a blend of hydrogenated diesel cuts. 
     
     
         10 ) The composition in accordance with one or more of the previous claims, wherein the petroleum component (A) comprises one or more diesel cuts in the mixture with a desulphurized gas oil cut coming from fluid bed catalytic cracking (LCO). 
     
     
         11 ) The composition according to  claim 1  or  2 , containing additives. 
     
     
         12 ) The composition according to  claim 11 , containing additives for improving the cold behaviour, anti-foam performance, cetane number improvers, antirust agents, detergents, additives for improving the lubricity, anti-oxidant agents, anti-wear agents, antistatic agents. 
     
     
         13 ) The composition according to  claim 1  or  2 , wherein the mixture of a biological origin (C) is a mixture of a vegetable or animal origin. 
     
     
         14 ) The composition according to  claim 1 ,  2  or  13 , wherein the esters of fatty acids, contained in the mixtures of a biological origin, are triglycerides of fatty acids, wherein the hydrocarbon chain of the fatty acid contains from 12 to 24 carbon atoms and is mono- or poly-unsaturated. 
     
     
         15 ) The composition according to  claim 14 , wherein the mixture of a biological origin can be selected from vegetable oils, vegetable fats, animal fats, fish oils or mixtures thereof. 
     
     
         16 ) The composition according to  claim 15 , wherein the vegetable oils or fats, possibly deriving from plants selected by genetic engineering, are selected from sunflower oils, rape oil, canola oil, palm oil, soybean, hemp, olive, linseed oil, charlock, peanuts, castor oil, coconut oil or fatty oils contained in pine wood (“tall oil”) recycled oils and fats from the food industry and mixtures thereof, and animal oils or fats are selected from lard, tallow, milk fats, recycled oils or fats of the food industry and mixtures thereof. 
     
     
         17 ) The composition according to  claim 1  or  2 , wherein the mixtures of a biological origin (C) are mixed with one or more hydrocarbons before being fed to step (1). 
     
     
         18 ) The composition according to  claim 1  or  2 , wherein step (1) is effected in the presence of hydrogen and a hydrogenation catalyst containing a carrier and one or more metals selected from the metals of groups VIII and VIB. 
     
     
         19 ) The composition according to  claim 18 , wherein the carrier for the catalyst of step (1) is selected from alumina, silica, zirconia, titania or mixtures thereof. 
     
     
         20 ) The composition according to  claim 18 , wherein the metal or metals contained in the catalyst of step (1) are selected from Pd, Pt, Ni or from the pairs of metals Ni—Mo, Ni—W, Co—Mo and Co−W. 
     
     
         21 ) The composition according to  claim 18 , wherein the catalyst of step (1) is selected from the catalytic compositions Ni—Mo—P on zeolite, Pd/Zeolite, Pt/MSA. 
     
     
         22 ) The composition according to  claim 1 ,  2  or  18 , wherein step (1) is carried out in a reaction zone comprising one or more catalytic beds, in one or more reactors. 
     
     
         23 ) The composition according to  claim 22 , wherein step (1) is carried out in a fixed-bed hydrotreating reactor. 
     
     
         24 ) The composition according to  claim 18 ,  22  or  23 , wherein in step (1) the streams of hydrogen and feedstock of a biological origin can be sent in equicurrent or countercurrent. 
     
     
         25 ) The composition according to  claim 18 ,  22 ,  23  or  24 , wherein the reactor has adiabatic layers in a number higher than or equal to 2. 
     
     
         26 ) The composition according to  claim 22 ,  23  or  25 , wherein a stream of hydrogen and/or liquid feedstock, at a defined temperature, is sent between one catalytic bed and another to obtain a constant or increasing temperature profile. 
     
     
         27 ) The composition according to  claim 18  or  22 , wherein the reactor is of the tube-bundle type, the catalyst is charged inside the tubes, and a diathermic liquid is sent into the mantle side. 
     
     
         28 ) The composition according to  claim 25  or  27 , wherein the reactor is run with the recirculation of part of the effluents. 
     
     
         29 ) The composition according to  claim 28 , wherein the recycling ratio, i.e. the amount of fraction recirculated with respect to the fresh feedstock, varies from 0.5 to 5 by weight. 
     
     
         30 ) The composition according to  claim 18 , wherein a slurry reactor is used, in which the hydrodeoxygenation catalyst is formed as microspheres and dispersed in the reaction environment, and the mixing is effected by mechanic stirring or by forced recirculation of the reaction fluids. 
     
     
         31 ) The composition according to  claim 1  or  2 , wherein step (1) is effected at a pressure varying from 25 to 70 bar, at a temperature ranging from 240 to 450° C. 
     
     
         32 ) The composition according to  claim 31 , wherein step (1) is carried out at a temperature ranging from 270 to 430° C. 
     
     
         33 ) The composition according to  claim 31 , wherein step (1) is carried out at a pressure ranging from 30 to 50 bar. 
     
     
         34 ) The composition according to  claim 31 , wherein step (1) is carried out at a LHSV ranging from 0.5 to 2 hr −1 . 
     
     
         35 ) The composition according to  claim 31 , wherein step (1) is carried out with a H 2 /mixture of a biological origin ratio ranging from 400 to 2,000 Nl/l. 
     
     
         36 ) The composition according to  claim 18  or  20 , wherein the catalysts based on Ni—Mo, Ni—W, Co—Mo and Co—W are sulphidated before being used. 
     
     
         37 ) The composition according to  claim 1  or  2 , wherein the mixture of a biological origin is subjected to a pretreatment before being fed to step (1), wherein said pretreatment is effected by means of adsorption, treatment with ion exchange resins or slightly acidic washings. 
     
     
         38 ) The composition according to  claim 1  or  2 , wherein the mixture resulting from step (1) is subjected to purification treatment before being hydroisomerized, wherein the purification treatment comprises a separation step and a washing step. 
     
     
         39 ) The composition according to  claim 38 , wherein, in the separation step, the mixture resulting from step (1) is sent to a high pressure gas-liquid separator, in order to recover a gaseous phase and a liquid phase. 
     
     
         40 ) The composition according to  claim 39 , wherein the gaseous phase, containing hydrogen, water, CO, CO 2 , light paraffins (C4 − ) and possibly small amounts of NH 3 , PH 3  and H 25 , is cooled, water and condensable hydrocarbons are separated by condensation, and the remaining gaseous phase is purified to obtain hydrogen which can be recycled to the reaction step (1). 
     
     
         41 ) The composition according to  claim 39 , wherein the liquid phase separated in the high pressure separator, formed by a hydrocarbon fraction, essentially consisting of linear paraffins with a number of carbon atoms varying from 14 to 21, is washed with hydrogen or nitrogen or a gaseous hydrocarbon, in a stripper, before being fed to the subsequent hydroisomerization step (2). 
     
     
         42 ) The composition according to  claim 1 , wherein step (2) is carried out in the presence of hydrogen and a catalytic system comprising one or more metals of Group VIII mixed with one or more metals of Group VI. 
     
     
         43 ) The composition according to  claim 2 , wherein step (2) is carried out in the presence of hydrogen and a catalytic composition which comprises:
 a) a carrier of an acidic nature comprising a completely amorphous micro-mesoporous silica-alumina having a SiO 2 /Al 2 O 3  molar ratio ranging from 30 to 500, a surface area greater than 500 m 2 /g, a pore volume ranging from 0.3 to 1.3 ml/g, an average pore diameter lower than 40 Å,   b) a metal component containing one or more metals of group VIII, possibly mixed with one or more metals of group VIB.   
     
     
         44 ) The composition according to  claim 2  or  43 , wherein in step (2) the silica-alumina contained in the carrier of an acidic nature (a), has a SiO 2 /Al 2 O 3  molar ratio ranging from 50 to 300. 
     
     
         45 ) The composition according to  claim 2  or  43 , wherein in step (2) the silica-alumina contained in the carrier of an acidic nature (a), has a porosity ranging from 0.3 to 0.6 ml/g 
     
     
         46 ) The composition according to  claim 2  or  43 , wherein in step (2) the component of an acidic nature (a) of the catalytic system is in the form of an extruded product containing a binder. 
     
     
         47 ) The composition according to  claim 46 , wherein in step (2) the component of an acidic nature (a) of the catalytic system in the form of an extruded product containing a binder, is prepared by means of a process comprising the following steps:
 (A) preparing an aqueous solution of a tetra-alkylammonium hydroxide (TAA-OH), a soluble aluminium compound capable of hydrolyzing into Al 2 O 3  and a silicon compound capable of hydrolyzing to SiO 2 , in the following molar ratios:   
       SiO 2 /Al 2 O 3  from 30/1 to 500/1 
       TAA-OH/SiO 2  from 0.05/1 to 0.2/1 
       H 2 O/SiO 2  from 5/1 to 40/1 
       (B) heating the solution thus obtained to cause its hydrolysis and gelification and obtain a mixture A with a viscosity ranging from 0.01 to 100 Pa sec; 
       (C) adding to the mixture A, first a binder belonging to the group of bohemites or pseudo-bohemites, in a weight ratio with the mixture A ranging from 0.05 to 0.5, and subsequently a mineral or organic acid in a quantity ranging from 0.5 to 8.0 g per 100 g of binder; 
       (D) heating the mixture obtained under point (C), under stirring, to a temperature ranging from 40 to 90° C., until a homogeneous paste is obtained, which is subjected to extrusion and granulation; 
       (E) drying and calcining the extruded product in an oxidizing atmosphere. 
     
     
         48 ) The composition according to  claim 2 , wherein in step (2) the catalytic system contains as metal component (b) one or more metals of Group VIII selected from Pt, Pd, Ni, Co. 
     
     
         49 ) The composition according to  claim 48 , wherein the catalytic system only contains metals of Group VIII and said metals are preferably selected from Pt, Pd and Ni. 
     
     
         50 ) The composition according to  claim 48 , wherein the catalytic system contains one or more metals of Group VIII and one or more metals of Group VIB, said metals of group VIII are selected between Ni and Co. 
     
     
         51 ) The composition according to  claim 2 ,  48  or  50 , wherein in step (2) the catalytic system contains as metal component (b) both one or more metals of group VIII and one or more metals of Group VIB, and the metal of Group VIB is selected from Mo and W. 
     
     
         52 ) The composition according to  claim 2 , wherein in the catalytic system of step (2) the metal of Group VIII is in a quantity ranging from 0.1 to 5% by weight with respect to the total weight of the catalyst. 
     
     
         53 ) The composition according to  claim 2 , wherein in the catalytic system of step (2) the metal of Group VIB is in a quantity ranging from 1 to 50% by weight with respect to the total weight of the catalyst. 
     
     
         54 ) The composition according to  claim 53 , wherein the metal of Group VIB is in a quantity ranging from 5 to 35% by weight. 
     
     
         55 ) The composition according to  claim 2 , wherein in step (2) the catalytic system comprises one or more metals of Group VIII and a carrier of silica gel and alumina, amorphous to X rays, having a SiO 2 /Al 2 O 3  molar ratio ranging from 30 to 500, a surface area in the range of 500 to 1000 m 2 /g, a pore volume ranging from 0.3 to 0.6 ml/g and a pore diameter mainly within the range of 10 to 30 Å. 
     
     
         56 ) The composition according to  claim 2 , wherein in step (2) the catalytic system comprises one or more metals of Group VIII and a calcined carrier of silica gel and alumina, amorphous to X rays, having a SiO 2 /Al 2 O 3  molar ratio ranging from 30 to 500, a surface area in the range of 500 to 1000 m 2 /g, a pore volume of up to 0.8 ml/g and an average pore diameter within the range of 10 to 40 Å. 
     
     
         57 ) The composition according to  claim 2 , wherein in step (2) the catalytic system contains one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re and a silica-alumina carrier, amorphous to X rays, having a SiO 2 /Al 2 O 3  molar ratio ranging from 30 to 500, a surface area greater than 500 m 2 /g, a pore volume ranging from 0.3 to 1.3 ml/g and an average pore diameter smaller than 40 Å. 
     
     
         58 ) The composition according to  claim 2 , wherein in step (2) the catalytic system comprises a blend of metals of Groups VIB and VIII and a carrier of silica gel and alumina, amorphous to X rays, having a SiO 2 /Al 2 O 3  molar ratio ranging from 30 to 500, a surface area in the range of 500 to 1000 m 2 /g, a pore volume ranging from 0.3 to 0.6 ml/g and a pore diameter within the range of 10 to 40 Å. 
     
     
         59 ) The composition according to  claim 2 , wherein the hydroisomerization step (2) is carried out in a fixed bed reactor. 
     
     
         60 ) The composition according to  claim 59 , wherein in step (2) the reactor is of the type with adiabatic layers. 
     
     
         61 ) The composition according to  claim 1 ,  59  or  60 , wherein the mixture subjected to hydroisomerization is fed to the reactor in equicurrent or countercurrent with respect to the hydrogen. 
     
     
         62 ) The composition according to  claim 61 , wherein the process is effected in countercurrent, in a reactor with a number of layers higher than or equal to 2, wherein the first layer, immersed by the mixture subjected to hydroisomerization, consists of a filler consisting of inert material or pellets or spherules of inert material. 
     
     
         63 ) The composition according to  claim 1 , wherein the hydroisomerization step (2) is carried out in the presence of hydrogen at a temperature ranging from 250 to 450° C. and a pressure ranging from 25 to 70 bar. 
     
     
         64 ) The composition according to  claim 2  or  43 , wherein the hydroisomerization step (2) is carried out at a temperature ranging from 250 to 450° C. and a pressure ranging from 25 to 70 bar. 
     
     
         65 ) The composition according to  claim 64 , wherein step (2) is carried out at a temperature ranging from 280 to 380° C. 
     
     
         66 ) The composition according to  claim 64 , wherein in step (2) the pressure ranges from 30 to 50 bar. 
     
     
         67 ) The composition according to  claim 64 , wherein step (2) is carried out with a LHSV ranging from 0.5 to 2 hr −1  and with a H 2 /HC ratio of between 200 and 1,000 hr −1 . 
     
     
         68 ) Use in a diesel composition, with the purpose of improving the cold properties, of a component of a biological origin containing esters of fatty acids and possibly aliquots of free fatty acids, by means of a process including the following steps: 
       1) hydrodeoxygenation of the mixture of a biological origin; 
       2) hydroisomerization of the mixture resulting from step (1), after possible water and gaseous stream separation, and possible purification treatment. 
     
     
         69 ) Use in a diesel composition, with the purpose of decreasing the quantity of additives for improving the cold properties, of a component of a biological origin obtained from a mixture of a biological origin containing esters of free fatty acids, by means of a process comprising the following steps: 
       1) hydrodeoxygenation of the mixture of a biological origin; 
       2) hydroisomerization of the mixture resulting from step (1), after possible water and gaseous stream separation, and possible purification treatment. 
     
     
         70 ) Use in a diesel composition, according to  claim 68  or  69 , of a component of a biological origin obtained from a mixture of a biological origin, containing esters of fatty acids and possibly aliquots of free fatty acids, by means of a process including the following steps: 
       1) hydrodeoxygenation of the mixture of a biological origin; 
       2) hydroisomerization of the mixture resulting from step (1), after possible water and gaseous stream separation, and possible purification treatment, said isomerization being effected in the presence of a catalytic system comprising: 
       a) a carrier of an acidic nature comprising a completely amorphous micro-mesoporous silica-alumina having a SiO 2 /Al 2 O 3  molar ratio ranging from 30 to 500, a surface area greater than 500 m 2 /g, a pore volume ranging from 0.3 to 1.3 ml/g, an average pore diameter lower than 40 Å, 
       b) a metal component containing one or more metals of Group VIII, possibly in a mixture with one or more metals of group VIB.