Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/617—500-1000 m2/g
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/12—Oxidising
  • B01J37/14—Oxidising with gases containing free oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
  • C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1014—Biomass of vegetal origin
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1018—Biomass of animal origin
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4012—Pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4081—Recycling aspects
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the present invention relates to the use of fatty substances with a iodine number greater than 135 gI 2 /l00g for the production of biodiesel, a method for producing biodiesel and the use of a catalyst for said production.
• Biodiesel may be represented chemically as a mixture of fatty acid methyl esters. It is a naturally derived liquid fuel, produced from renewable sources which, in compliance with appropriate prescriptions, may be used in place of diesel fuel for both internal combustion engines and for producing heat in boilers .
• the advantages, especially environmental, which can potentially result from the widespread use of biodiesel, are manifold:
• biodiesel is one of the fuels whose use should allow the objectives envisaged in the Kyoto agreement to be achieved; • considering the fact that the triglyceride oils used for the production of biodiesel are sulphur free, and that sulphur is not added to the end product in any way, the use of biodiesel does not contribute towards the phenomenon of acid rain;
• biodiesel is biodegradable and allows reduced emissions, in terms of particulates and polycyclic aromatic hydrocarbons .
• results of the combustion of biodiesel are contentious in relation to so-called NOx emissions, where it has been observed that such emissions are more or less increased, with respect to conventional diesel, depending on the characteristics of the engine in which it is used; • for economies like the European economy, which has to sustain the demand for energy with massive imports of fossil fuels, this is an excellent opportunity to have available an autonomous, as well as renewable energy source.
• the European Union strongly encourages this initiative, which allows the use of marginal land, not dedicated to food production, with undoubted advantages for safeguarding and increasing the work force and protecting and safeguarding the environment .
• biodiesel marketed for consumption must comply with the various prescriptions made official through the European standards EN 14213:2003 and EN 14214:2003, which establish the minimum characteristics biodiesels must possess for use in boilers and haulage, respectively.
• biodiesel would be a good alternative to diesel fuel of fossil origin, but its production still has a number of problems, including the following:
• the present invention relates to the use of fatty substances having a iodine number greater than 135 gI 2 /l00g, preferably greater than
• the invention relates to a method for the production of biodiesel, using fatty substances having a iodine number greater than 135 gI 2 /l00g, preferably greater than 140 gI 2 /l00g, more preferably greater than 150 gI 2 /l00g, as starting product.
• the fatty substances preferably used for the purposes of the invention are tall oil and high degree of unsaturation vegetable and animal oils .
• the animal oils are preferably fish oils.
• Tall oil is a by-product of the paper industry, whenever this is prepared according to the KRAFT process.
• Said material consists of a mixture of highly unsaturated fatty acids (many of which with conjugated diene systems) and terpene derived resin acids, such as abietic acid (C 2O H 30 O 2 ) and pimaric acid (C 20 H 30 O 2 ) .
• the resin acids are present in concentrations even exceeding 30 % m/m.
• Tall oil has a iodine number equal to approx. 170 gI 2 /l00 g.
• Linseed oil has a high content of C18:3, fatty acids with a high degree of unsaturation. Indeed, the iodine number of linseed oil is around 170 gI 2 /l00 g.
• the fish oil used for the purposes of the invention is preferably obtained from the processing of fish waste.
• Fish oil also has a iodine number equal to around 170 gI 2 /l00 g and is made up of polyenes such as C18:4, C20:4, C20:5, C22 : 5 and C22:6.
• the fatty acids constituting the fatty substances having a iodine number greater than 135 gI 2 /l00g have an excessively high degree of unsaturation, making such substances unsuitable for the preparation of biodiesel conforming to the reference standards.
• This fact, together with the conspicuous presence of conjugated diene systems, is the cause of the marked reactivity of the fatty acids of such substances which, when considered in relation to biodiesel, explain the very low or non-existent resistance to oxidation.
• resistance to oxidation is one of the main factors which qualify a biodiesel as being of good quality.
• the major fatty acids present in the plant-derived fatty substances of the invention are linolenic acid (9, 12, 15-octadecatrienoic, C 18:3), linoleic acid (9,12- octadecadienoic, C18:2) and the conjugated isomers thereof and oleic acid (9-octadecenoic, C18:l).
• Their rates of oxygen absorption are 800:100:1 respectively, hence partial hydrogenation with consequent lowering of the iodine number would lead to a significant increase in oxidative stability, particularly when C18:3 is reduced.
• Analogous considerations are valid for the reduction of the polyunsaturated components (up to 6 double bonds) of fish oil.
• the degree of unsaturation of the fatty acids is normally expressed as the iodine number, i.e. the number of grams of iodine that have reacted with 100 g of product analysed.
• the higher the index (number) the greater the degree of unsaturation.
• a maximum iodine number limit is envisaged of 120 gI 2 /l00g, while, as already mentioned, the fatty substances of the invention have a iodine number greater than 135 gI 2 /l00g.
• Table 1 The influence of double bonds number, position and geometry on the melting points of the 18 carbon atom fatty acids
• fatty substances having iodine numbers greater than 135 gI 2 /l00g, preferably- greater than 140 gI 2 /l00g, more preferably greater than 150 gI 2 /l00g, for the production of biodiesel it is essential to have a hydrogenation catalyst which reduces the degree of unsaturation by as much as possible, without however increasing the stearic acid content and limiting cis-trans and positional isomerisation by as much as possible.
• tall oil it is essential to reduce the resin acid content, which results in increased Conradson Carbon Residue with consequences for the good operation of the fuel, by as much as possible.
• oils may be used as plasticisers and vulcanisation activators (Kauchuk i Rezina, 1996, in Russian, CAM 126:331500).
• the fatty substances of the invention besides a high linoleic acid (C18:2) content, also have a significant amount of conjugated diunsaturated acids
• the present invention relates to a method for the production of biodiesel consisting of the following steps: a) esterification of the fatty acids or transesterification of the triglycerides of fatty substances having a iodine number greater than 135 gI 2 /l00g, preferably greater than 140 gI 2 /l00g, more preferably greater than 150 gI 2 /l00g, with a Ci-C 10 alkyl alcohol, optionally in the presence of a suitable catalyst ; b) selective hydrogenation of the fatty acid alkyl esters obtained in step a) in the presence of a catalyst, allowing the attainment of a biodiesel with a degree of unsaturation less than or equal to 120 gl 2 / 100 g and which is liquid at temperatures greater than or equal to -20 0 C.
• the preferred starting product for the method of the present invention is tall oil, vegetable or animal oils, preferably fish oils. Whenever tall oil is used, this preferably has a resin acid content ranging between 1 and 25% m/m, preferably between 1 and 15% m/m, and more preferably between 2 and 7% m/m. Furthermore, tall oil may optionally be distilled prior to use in the method of the invention, so as to reduce the resin acid content.
• Tall oil colophony (rosin) a mixture of resin acids with varying degrees of purity, which finds a number of uses in those industries using natural resins for the production of lacquers, paints, hydrophobic coatings, inks, loads for plastics etc., is obtained as a by-product of said distillation.
• step a) preferably has from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms and even more preferably, is methyl alcohol .
• step a) is a transesterification step, carried out according to the procedures of the known art .
• step a) is an esterification step, preferably carried out in the presence of a homogeneous or heterogeneous catalyst.
• the homogeneous catalyst is an acid compound, for example concentrated sulphuric acid, p- toluenesulphonic acid monohydrate, gaseous hydrochloric acid, phosphoric acid or methanesulphonic acid.
• the heterogeneous catalyst is advantageously a metallic oxide selected from: ZnO, SnO, CaO.
• a homogeneous catalyst is preferably used for the esterification reaction of step a) .
• the high degree of unsaturation fatty acids are mixed with an excess of the alkyl alcohol and the catalyst, and the reaction is initially carried out at the boiling point of the alkyl alcohol used. Due to the formation of water, the temperature increases over the course of the reaction.
• the mixture is neutralised through the addition of a suitable base, for example NaOH. This leads to the formation of a salt, which precipitates from the mixture and must be separated out, for example by means of filtration.
• a heterogeneous catalyst is used, then upon completion of the reaction, the solid catalyst is separated from the reaction mixture, for example by means of filtration, and all the operations necessary for the recycling of the catalyst are performed, for example washing and drying.
• the excess alkyl alcohol and water mixture is separated from the mixture containing the reaction product (i.e. the high degree of unsaturation fatty acid alkyl esters) and the unreacted resin acids, in the case of tall oil, by means of evaporation under vacuum.
• the water is then removed from the alkyl alcohol by means of distillation, and the alkyl alcohol recovered and recycled.
• the reaction of step a) may be carried out at temperatures greater than the boiling point of the alkyl alcohol, for example at approx. 150 0 C, thus increasing the pressure appropriately. This solution is preferred whenever a heterogeneous catalyst is used.
• the reaction may be carried out in two or more steps with the intermediate elimination of the water and alkyl alcohol, and the regeneration of the alcohol alone.
• the resin acids present in the starting product are not esterified and may be separated and recovered in step al) thanks to the differences in volatility.
• the separation of the fatty acid alkyl esters obtained in step a) from the non-esterified resin acids is advantageously carried out by means of distillation under vacuum using suitable discontinuous distillation equipment, or in continuous stills, for example thin film stills.
• the preferred distillation temperature is between 140 and 220 0 C, preferably between 180 and 200 0 C.
• the residual pressure is between 1 and 10 mbar, preferably between 1 and 5 mbar.
• Distillation is preferably performed after having heated the starting product to a temperature of approx. 100 0 C under vacuum, for the amount of time required for its complete degassing and anhydration.
• This operation accomplishes two main objectives: i) the forced removal of the resin acids, thus allowing the use of only partially refined tall oil, and hence the use of low cost raw materials; ii) a potential reduction in the Conradson Carbon Residue; iii) a thorough cleaning of the substrate prior to moving onto the selective hydrogenation of step b) , thus allowing the standardisation of the experimental hydrogenation conditions, as well as reduced amounts of hydrogenation catalyst which, by being able to operate in a clean environment and with reduced concentrations of agents inhibiting its activity, may easily be reused in the case of batch reactions, or with its operational lifespan foreseeably being increased in the case of continuous embodiments.
• Step al) involving the distillation of the resin acids, is not performed when other fatty substances, such as for example vegetable oils and fish oil, not containing such resin acids, are used as the starting products.
• the process thus proceeds directly to the selective hydrogenation of the fatty acid alkyl esters produced in step a) , which leads to the forced removal of the conjugated polyene, triene or diene systems, the reduction of the linoleic acid alkyl ester content and thus an overall reduction of the iodine number, to numbers of less than the 120 gI 2 /l00g limit, and may further be adjusted and targeted, depending on the qualitative characteristics of the desired final product .
• a copper catalyst supported on a suitable solid support is copper supported on Al 2 O 3 , SiO 2 , sepiolite and TiO 2 .
• the catalyst of the invention is copper supported on Al 2 O 3 , sepiolite and TiO 2 . Even more preferably, it is Cu/Al 2 O 3 .
• selective hydrogenation is carried out in any of the reactors known in the art, into which the catalyst and the fatty acid alkyl ester mixture produced in step a) or al) are introduced.
• the mixture is kept stirring and under a positive pressure of hydrogen of from 2 to 8 atm, preferably around 6 atmospheres. It is heated to a temperature of between 150 to 200 0 C, preferably around 180 0 C.
• the reaction times range between 30 minutes and 4 hours, preferably between 1 and 3 hours.
• the catalyst is preferably washed, dried and recycled.
• the present invention relates to the use of a copper catalyst supported on a suitable solid support for the selective hydrogenation of the fatty acid alkyl esters of fatty substances having iodine numbers greater than 135 gI 2 /l00g, preferably greater than 140 gI 2 /l00g, more preferably greater than 150 gI 2 /l00g.
• the catalyst used in the present invention allows the removal of the conjugated and isolated polyenes and dienes with the formation of monoenes, without in any way achieving the complete saturation of the molecule, with the consequent formation of saturated fatty acids .
• the catalyst of the present invention is copper supported on Al 2 O 3 , SiO 2 , sepiolite and TiO 2 . More preferably, the catalyst of the invention is copper supported on Al 2 O 3 , sepiolite and TiO 2 . Even more preferably, it is Cu/Al 2 O 3 .
• the silica used in the present invention is preferably mesoporous silica having a specific surface area ranging between 200 m 2 /g and 650 m 2 /g, preferably between 300 and 600 m 2 /g.
• Said silica has a pore volume (PV) ranging between 0 and 2 ml/g, preferably between 0.8 and 1.2 ml/g.
• the alumina used in the present invention preferably has a specific surface area ranging between 100 m 2 /g and 500 m 2 /g, preferably between 200 and 350 m 2 /g.
• Said silica has a pore volume (PV) ranging between 0.5 and 2 ml/g, preferably between 1 and 2 ml/g.
• the sepiolite used in the present invention has a surface area of approx. 240 m 2 /g and PV of approx.
• the catalyst of the invention is prepared by treating an aqueous solution of Cu 2+ ions with a fine base, so as to obtain a clear solution.
• the solid support is then added, and the mixture kept stirring for from 15 minutes to 2 hours, preferably for approx. 20 minutes .
• the solution is diluted so as to cause the deposition of the hydrogenolysis product onto the support, and the solid is separated from the solution by means of filtration, then dried and calcined in air.
• Drying occurs at a temperature of between 110 and 150 0 C, preferably around 120 0 C, for a length of time ranging between 6 and 24 hours, preferably for approx. 12 hours. Calcination is carried out at a temperature ranging between 300 and 400 0 C, preferably at approx. 350 0 C, for a period of time ranging between 1 and 10 hours, preferably for approx. 3 hours.
• the precursor of the catalyst thus obtained Prior to the selective hydrogenation of the fatty acid alkyl esters, the precursor of the catalyst thus obtained must be activated by air drying at a temperature ranging between 200 and 300 0 C 7 preferably around 270 0 C, for a period of time ranging between 15 minutes and 2 hours, preferably for approx. 20 minutes.
• the reactor is subsequently closed and evacuated at the same temperature and for the same length of time. At the same temperature, H 2 is then introduced, and then all the water formed removed under vacuum. In order to be certain of having reduced all the metal oxide present, it is preferable to repeat the vacuum/H 2 cycle a second time.
• the present invention allows the use of high iodine number fatty substances as starting materials for the production of biodiesel, with the consequent advantages of using raw materials that are widely available and cheap, hence, providing a low cost fuel, the production cost of which is not influenced by problems associated with the marketing and/or disposal of glycerine, when the raw material used is tall oil.
• the biodiesel production process according to the invention allows the recycling of the reagents and by-products, such as the alkyl alcohol, the catalysts and the water, all to the benefit of the environment .
• the catalyst used in the present invention allows the removal of polyenes with the formation of monoenes, without in any way achieving the complete saturation of the molecule, with the formation of saturated fatty acid esters.
• a positive side effect of this treatment, in relation to the use of tall oil, is a further reduction in the Conradson Carbon Residue, which can be explained by a reduction in diene systems (particularly conjugated systems) and thus the tendency of the mixture to polymerise, allowing the vaporisation and combustion of the molecules before said thermal polymerisation can occur .
• the mixture has been diluted so as to cause the decomposition of the finely dispersed hydrogenolysis product onto the support .
• the material has been separated by filtration, dried for 12 hours at
• the precursor Prior to the reaction, the precursor has been activated by air drying at 270 0 C for 20 minutes.
• the reactor has been subsequently closed and evacuated at the same T (temperature) for a further 20 minutes, then H 2 (1 atm) has been introduced, and still at 270 0 C, all the water formed has been removed under vacuum.
• Catalysts A' and B' have thus been prepared starting from precursors A and B. Synthesis of the biodiesel
• the reaction is carried out in a reactor fitted with a stirrer, a temperature monitoring and control device, a reflux condenser and an access way for withdrawing samples.
• the reaction is normally carried out at the mixture's boiling point, which initially coincides with that of pure methyl alcohol (64 0 C) , then being increased in parallel with the degree of progress of the reaction, due to the water formation. Said temperature increase is more sensitive the more the stoichiometric excess used is reduced. The progress of the reaction is followed by means of periodic sampling and the determination of the residual acidity.
• the residual acidity is neutralised through the addition of an aqueous solution of NaOH, and the excess methyl alcohol used, which is evaporated along with the water produced during the esterification reaction, recovered.
• the hydroalcoholic mixture is then sent to be separated by distillation, for the purification of the methyl alcohol to be recycled in the system, and the isolation and elimination of the reaction water.
• the mixture of methyl esters Prior to performing the distillation step under vacuum, the mixture of methyl esters is subjected to filtration in order to eliminate any insoluble sodium sulphate (sodium para-toluenesulphonate) deriving from the neutralisation of the catalyst.
• the mixture of tall oil fatty acid methyl esters as described in example A (above) is transferred into the high vacuum distillation apparatus fitted with a multi-necked round- bottomed flask with connections for monitoring the temperature, residual pressure, the mechanical stirring system, Claisen type vapour spray retention manifold, Liebig type indirect heat exchange condenser system, distillate collection device and high vacuum pump, of suitable capacity.
• the simple distillation operation conducted after having maintained the product at a temperature of approx. 100 0 C under vacuum, for the entire time necessary for its degassing and anhydration, is typically performed at a temperature of 180-200 0 C and at a residual pressure of 1-2 mbar (0.1 KPa) .
• the yield of the process depends on the resin acid content of the starting product.
• the distillation operation allowed the reduction of the resin acid content of the methylated sample from 6.7 % (m/m) to 0.67 % of the sample prepared for distillation.
• the remaining 12.6% by weight not indicated in the table was constituted by palmitic, palmitoleic and erucic acids, which remain unaltered during the hydrogenation.
• the reactor has been pressurised with H 2 (6 atm) the temperature adjusted to 180 0 C and the reaction mass subjected to stirring. Samples are withdrawn at 20 minute intervals, and analysed. When the analysis seems to satisfy the requirements (80 min.) the reactor is cooled and the mixture analysed to give the iodine number, the flow point, the Conradson carbon residue (0.01 %) and the Cu content (not detectable). The results are reported in Table 3.
• Example 4 Hydrogenation of linseed oil methyl esters with catalyst B (step b) ) , obtained by means of transesterification according to the known art.
• SM2 linseed oil methyl esters
• SM3 fish oil ethyl esters

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