Classifications

• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
  • B01J23/04—Alkali metals
• • 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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • 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
• • 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
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • 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

Definitions

• glycerol ethers are also potential fuel additives that can enter the diesel fuel pool.
• Transesterification with ethanol is generally less effective.
• transesterification with ethanol is slower than with methanol, methanol being more acidic than ethanol.
• one of the reasons given relates to the better solvent power of ethanol which is responsible for the poor separation of glycerin from the reaction medium.
• the transesterification being a balanced reaction, the solubilization of glycerol in the reaction medium may have the effect of limiting the rate of progress of the reaction.
• Glycerol ethers are potential fuel additives that can be used in fuel formulation. This application is all the more interesting as European directives will require in 2010 the use of 5.75% of biofuels in transport.
• International application WO 2007/061903 A1 (CPS biofuels) and US Pat. No. 5,308,365 (ARCO Chemical Technology) describe fuel compositions comprising glycerol ethers.
• glycerol ethers can replace conventional oxygen additives of the MTBE type. They also reduce particulate emissions and reduce the viscosity of biodiesel fuel. It is also reported that the presence of the hydroxyl group of partially etherified glycerol ethers may allow the incorporation of small amounts of water into the fuels, which would reduce NOx emissions. From WO 2005/093015 (IFP), it is known that glycerol ethers make glycerol soluble in biodiesel. In this patent application obtaining a mixture of mono, di and tri-glycerol ethers is described, the mixture being soluble in biodiesel.
• etherification of glycerol with methanol or isopropanol in the presence of an Amberlyst resin is reported.
• Processes for producing biodiesel have been described using two distinct steps including a step of etherification of glycerol.
• the first step is a transesterification reaction of a vegetable oil with an alcohol, in the presence of a cyanide double metal catalyst, the reaction medium is then cooled and reacted with the alcohol in the presence of an Amberlyst type catalyst.
• This transesterification process also has the disadvantage of using catalysts of the supported heteropoly acid type which are leachable catalysts and whose the activity and strength depend on the nature of the support and the acidic charge on the support.
• the object of the present invention is a process for producing a biodiesel by transesterification and etherification reaction in a single step of a vegetable oil with ethanol.
• Another objective of the present invention is a process for producing a biodiesel for the recovery of the secondary products formed and in particular glycerol.
• Another object of the present invention is a biofuel comprising ethyl esters of fatty acids and a mixture of ethyl ethers of glycerol.
• heterogeneous strong Bromsted acid catalysts heteropoly acid salts
• the inventors have discovered that it is possible to valorize all the secondary products forming during the reaction and in particular to etherify the glycerol, in a single step simultaneously with the transesterification reaction.
• the transesterification of the oils with an alcohol generates in situ glycerol in the reaction medium, which is converted into alkyl ethers of glycerol in the presence of a heterogeneous acid catalyst able to catalyze the transesterification and etherification reactions with the same alcohol .
• heterogeneous acid catalysis over conventional methods of homogeneous basic catalysis is of major interest in the recovery of oils that are potentially acidic, for example used oils which may have a high free acid content and which may contain traces of water more or less important.
• a basic solid catalyst will be capable of adsorptive deactivation of the free fatty acids on its surface when using oils with a high acid number.
• fatty acid esters and glycerol ethers are components of biofuels, all of a fat can be converted into diesel fuel without having to separate and purify glycerol, which has a huge cost advantage over compared to the processes of the prior art. Indeed, the process according to the invention makes it possible to eliminate the costly steps of isolating and purifying glycerol.
• the glycerol ethers formed are the most favorable vis-à-vis the reduction of NOx emissions. Moreover, by simply considering that the glycerol produced by transesterification of the oils represents of the order of 10% by weight of the fatty acid esters produced, the process according to the invention allows a yield increase of more than 15% by weight. .
• the use of the same catalyst to carry out the transesterification and the etherification on the one hand, and the same reagent, namely an alcohol, to carry out the two reactions, also represents an economic advantage. It is not necessary to use another olefin reagent to synthesize glycerol ethers.
• the solid catalyst used does not undergo the leaching observed on the supported acid-based catalysts, resists leaching and can therefore be easily isolated from the biofuel formed.
• the process does not require glycerol separation step, allows the use of alcohol with high solvent power, such as ethanol, which is advantageous because this Alcohol is "biobased", is a by-product of agricultural waste valorization channels, available at low cost and is not toxic in relation to methanol.
• the process allows the recovery of any secondary products that may be formed during the reaction.
• the present invention relates to a process for preparing a biofuel blend comprising fatty acid esters and at least one mixture of glycerol ethers from fats and ethanol comprising: a) a transesterification step of a vegetable or animal oil with ethanol in the presence of a catalyst based on at least one alkaline salt or ammonium heteropoly acid characterized by a differential heat of ammonia absorption greater than or equal to 150 KJ / mol, to obtain esters of fatty acids and glycerol, and, b) a step of etherification of the glycerol formed in step a) with the ethanol used in step a) in the presence of the catalyst of step a) to obtain at least one glycerol ether, said steps a) and b) taking place simultaneously, in a single reactor.
• the catalyst based on at least one alkaline salt or ammonium heteropoly acid is insoluble in the reaction medium and the biofuel obtained. In one embodiment, the catalyst is a catalyst based on at least one alkaline salt of heteropoly acid.
• the catalyst is a catalyst based on at least one ammonium salt of heteropoly acid.
• the differential heat of ammonia absorption is greater than 170 KJ / mol.
• the differential heat of ammonia absorption is greater than 190 KJ / mol.
• the glycerol reagent for step b) corresponds to a product of step a). It is an intermediate product not isolated.
• the method according to the invention advantageously makes it possible not to isolate and purify the glycerol to transform it into ethyl ether of glycerol (component of the biofuel).
• the expression "the steps a) and b) take place simultaneously” means that the two reactions take place simultaneously in the reaction medium ("one pot” reaction), the glycerol formed during step a) being converted into the ether of glycerol as soon as it forms.
• the reaction medium obtained at the end of the process may be glycerol-free if the conversion is continued by means known to those skilled in the art, namely increasing the reaction time. , the catalyst mass or by recirculation of the reaction medium.
• glycerol propane -1,2,3-triol.
• Glycerol can be pure glycerol, but also glycerol containing impurities, including water, inorganic salts (chloride, phosphate, sulfate, acetate), organic compounds (fatty acids, fatty acid esters, derivatives of ... glycerides). These impurities can represent from 5 to 95% by weight relative to the weight of glycerol.
• glycerol may be crude glycerol obtained by transesterification of vegetable or animal oils in the context of production of biodiesel.
• crude glycerol means glycerol obtained by simple decantation of the reaction medium at the end of the transesterification of vegetable or animal oils.
• glycerol etherification is meant the chemical reaction that transforms glycerol into glycerol ethers.
• glycerol ethers is meant the mono-, di- and tri-ethers of glycerol.
• the ether function (s) can be located at any position (s) 1, 2 or 3.
• the reaction of formation of the different glycerol ethers follows a successive path: mono and then di and tri-ether of glycerol are produced: it is possible to promote the formation of di and sorting by increasing the contact time reagents / catalyst (for example by increasing the catalyst mass or the reaction time) or the reaction product can be re-circulated to increase the conversion of glycerol and to direct the production of glycerol tri-ethers.
• the mixture of ethers obtained glycerol must simply be soluble in biodiesel or other fuels such as diesel (ex-oil) or gasoline (or bioethanol) in which it will be added.
• glycerol ethers means the mono and di-ethers of glycerol.
• ethanol in particular absolute and / or anhydrous ethanol.
• heteropoly acid is meant a compound consisting of hydrogen and oxygen with metallic elements (such as tungsten, molybdenum or vanadium) and non-metallic, generally derived from the block p of the periodic table (such as silicon , phosphorus or arsenic).
• the invention relates to a method, characterized in that the glycerol ethers are chosen from mono and di-ethers of glycerol. In one embodiment, the invention relates to a process in which the molar ratio between ethanol and vegetable or animal oil is between 1 and 50, preferably between 3 and 20. In one embodiment, the invention relates to a method of etherification of glycerol with ethanol comprising a reaction step between glycerol and ethanol in the presence of a catalyst based on at least one alkaline salt or ammonium heteropoly acid characterized by a differential heat of ammonia adsorption greater than or equal to 150 KJ / mol.
• the invention relates to the processes, characterized in that the catalyst based on at least one alkaline salt or ammonium of heteropoly acid at a differential heat of ammonia absorption greater than or equal to 170 KJ / mol, preferably greater than or equal to 190 KJ / mol.
• alkali or ammonium salts of heteropolyacids it is advantageous to use an alkaline or ammonium salt of solid heteropoly acid having the general formula:
• X represents a heteroatom selected from the group consisting of the following elements: P, Si, Ge, B or As; M represents a peripheral metal element selected from the group consisting of W, Mo or V; heteroatoms and represents 1 or 2,
• k is the number of hydrogen atoms and is between 1 and 10,
• m is the number of peripheral metal atoms W, Mo, V, and is between 1 and 20,
• the number of oxygen atoms and is between 2 and 62,
• the number of hydration water molecules is between 0 and 40, preferably between 6 and 30.
• the salts of heteropoly acids, strong Bronsted acid solids are selected from the group consisting of salts of heteropoly acids selected from the group consisting of H 3 PW 12 O 40 , 24H 2 O, H 4 SiW 12 0 40 , 24xH 2 O, H 6 P 2 W 18 O 62, 24H 2 O, H 5 BW 12 O 40, 30H 2 O, H 5 PW 1O V 2 O 4O xH 2 O, H 3 PMO 12 O 40, 28H 2 O, H 4 SiMo 12 O 40 , 13H 2 OH 3 PMo 6 V 6 O 40 XH 2 O or H 5 PMo 10 V 2 O 40, xH 2 O.
• heteropoly acid in the form of salt has many advantages, particularly from an industrial point of view, on the one hand, in contrast to the supported heteropolyacids (used in particular by Bokade et al), to avoid any problem of leaching of the active phase.
• the activity of the heteropoly acid salts does not depend on the support or the acidic charge on the support.
• the salts are alkali metal salts selected from Cs + , K + , or Rb + or ammonium salts (NH 4 + ).
• the salt is Cs + .
• the salt is a K + .
• the salt is an Rb + .
• the salt is an ammonium salt (NH 4 + ).
• NH 4 + ammonium salt
• differential heat of ammonia adsorption is meant the molar heat released by the adsorption of infinitesimal doses of ammonia, at a constant temperature, on the catalyst initially under vacuum in a calorimeter of Tian-Calvet type.
• ammonia adsorption differential heat values correspond to the value of the plateau of the curve representing the variation of the differential heats (Q diff kJ.mol-1) as a function of the quantity of ammonia adsorbed if the acidic solid has homogeneous sites in strength. If the differential heats decrease with the ammonia recovery, the value considered is the average of the adsorption differential heats at 50% ammonia recovery.
• Biofuel refers to a fuel produced from renewable organic materials.
• Biofuel blending means a mixture of biofuels or a “biobased” base for the formulation of other fuels.
• fatty acids denotes aliphatic carboxylic acids having a carbon chain of 4 to 28 carbon atoms.
• fat is meant natural fats of all origins.
• vegetable or animal oil is meant oil of animal or vegetable origin, such as the oil of microalgae, Pongamia pinnata (or Karanj), Jatropha, palm, sunflower, rapeseed, rapeseed. almond, peanut, coconut, flax, maize, olive, castor grapes, sesame or mustard, but also used oils rich in free acids. These oils contain or consist of acylglycerols, also called glycerides, which are esters of fatty acids and glycerol.
• acylglycerols There are three subclasses of acylglycerols: mono-, di- and triglycerides. The prefixes mon, di, and tri are used depending on whether the esterification relates to 1, 2 or 3 hydroxyl groups of glycerol.
• transesterification of vegetable or animal oil with an alcohol is meant the chemical reaction of the triglycerides with an alcohol in the presence of the catalyst to obtain esters of fatty acids and glycerol.
• etherification of glycerol with an alcohol is meant the reaction of glycerol and an alcohol in the presence of catalyst to obtain at least one ether of glycerol, which may be a mono-, di- or tri-ether of glycerol. Generally, a mixture of these ethers is obtained.
• the molar ratio between the ethanol and the vegetable or animal oil is between 1 and 50, in particular between 3 and 20, for example 4, 6, 12 or 18.
• the processes are carried out at a temperature of between 100 and 300 ° C., in particular 150 ° to 250 ° C., in particular around 200 ° C., and at a pressure of between 5 and 100 bar, in particular 10 to 75 bar. in particular 10 to 50 bar, more particularly between 20 and 30 bar.
• These reaction conditions are particularly suitable for carrying out the processes according to the invention, in particular the etherification of glycerol by ethanol, which is energetically demanding: it requires the use of an alkaline salt or ammonium-type catalyst.
• heteropoly acid at a reaction temperature of the order of 200 ° C.
• This temperature is well above the limit temperature for use of Amberlyst acid resins which is less than 150 ° C.
• the use of such catalysts is advantageous. because they are stable at these high temperatures, unlike other catalysts, such as Amberlyst type acid resins. In addition these catalysts are more reactive, for comparison, at 85 ° C the cesium heteropoly acid salt is 4 times more active than the Amberlyst 15 in relation to its more energetic sites.
• the present invention relates to the use of a catalyst based on at least one alkaline salt or ammonium of heteropoly acid to carry out an etherification of glycerol with ethanol, in which the catalyst based on 'at least one Alkaline or ammonium salt of heteropoly acid is characterized by a differential heat of ammonia absorption greater than 150 KJ / mol and stable at a temperature of 200 ° C.
• the catalyst is a catalyst based on In at least one alkaline salt of heteropoly acid, in one embodiment the catalyst is a catalyst based on at least one ammonium salt of heteropoly acid.
• the invention also relates to the use of a catalyst based on at least one alkaline salt or ammonium heteropoly acid to carry out simultaneously: a transesterification of a vegetable or animal oil with ethanol to obtain ethyl esters of fatty acids and of glycerol, and etherification of said glycerol with ethanol, in which the catalyst based on at least one alkaline salt or of ammonium of heteropoly acid is characterized by a differential heat of ammonia absorption greater than 150 KJ / mol, stable at a reaction temperature of
• the catalyst is a catalyst based on at least one alkaline salt of heteropoly acid.
• the catalyst is a catalyst based on at least one ammonium salt of heteropoly acid.
• the invention relates to a biofuel comprising ethyl esters of fatty acids and a mixture of ethyl ether of glycerol. In one embodiment, the invention relates to a biofuel comprising a mixture of mono and diethyl ethers of glycerol.
• said biofuel also comprises ethanol.
• the reaction conditions were as follows.
• the molar ratio [ethanol or tertiobutanol] / glycerol was 4.
• the reaction time was 3 hours.
• the results are shown in Table 1. The conversion is calculated according to the following equation:
• Gly represents the amount of glycerol, 0 GIy the amount of glycerol in the beginning of reaction and the amount of Gly f end of the reaction glycerol.
• Mono-ether selectivity 100 x mono-ether / (GIy 0 - Gly f )
• Tri-ether yield 100 x tri-ether / GIy 0
• HPA H 3 PW 12 O 40 and more precisely 40% by weight of 3PW 12 O 40 dispersed on supports.
• reaction conditions were as follows. 0.39 g of catalyst was used.
• the temperature was 200 ° C.
• the reaction time was 6 hours.
• Table 3 Conversion and selectivity of the etherification reaction of glycerol with ethanol according to the catalyst.
• Tables 2 and 3 show that whatever the catalyst used the etherification of glycerol by ethanol is energetically more demanding than etherification with tertiobutanol and therefore more difficult to achieve.
• the results of Tables 2 and 3 also show a variability of the activity of the heteropoly acids supported according to the support,
• reaction conditions were as follows. 0.5 g of Cs 2 HPW 12 O 40 catalyst were used (pretreatment: 1 h under vacuum at 200 ° C.). 0.2047 mol of ethanol and 0.01144 mol
• Triglyceride conversion 100 x (Tri o- Tri f ) / Tri o or ⁇ rdti
• Example 4 Reaction between rapeseed oil and ethanol in the presence of Cs 2 HPW 12 O 40 to produce in one step fatty acid ethyl esters (biodiesel) and glycerol ethers (ether-fuels).

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