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
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
  • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
• • 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
• • 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
• • 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
• • 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
  • 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 invention relates to a process for the production of biofuels from triglycerides leading to a mixture of fatty acid monoesters and soluble glycerol derivatives, namely ethers and / or glycerol acetals.
• biofuels means fuels or constituents for fuels consisting of (or comprising) one or more products, in particular oxygenated products, having a natural origin.
• Biodiesel denotes more particularly a fuel or a fuel constituent for diesel engines consisting of (or comprising) at least one alkyl ester of fatty acid of natural origin, such as a mixture of methyl esters of oil. vegetable (rapeseed, sunflower, etc.).
• the foreseeable massive development of Biodiesel will lead to the production of a quantity of glycerol equivalent to approximately 10% by mass of the Biodiesel produced. For example, an increase in Biodiesel production of
• glycerol is neutral, that it contains no salt or mineral or metallic compound and that its water content is very low.
• crude glycerol obtained from conventional Biodiesel manufacturing processes does not meet these requirements.
• conventional Biodiesel manufacturing processes use generally basic homogeneous catalysts, for example soda, potash, sodium or potassium alcoholates, such as sodium methylate. These catalysts, after reaction of transesterification of the triglyceride into methyl ester by methanol for example, are found both in the ester, generally in the form of metallic soaps / carboxylates, for example of sodium, and also in the co-produced glycerol in the form of alcoholate, for example sodium or potassium.
• the glycerol obtained contains catalyst or most often a compound derived from the catalyst, for example sodium or potassium glycerate.
• the glycerol also contains water in proportions which can range from a few% to for example 35% depending on the process used.
• the crude glycerol thus obtained from conventional processes for the production of Biodiesel cannot be directly used to be chemically modified by an olefin such as isobutene to lead to mixtures of ethers, since this reaction requires a neutral glycerol therefore free alkoxide.
• the presence of water is unfavorable for the proper conduct of this reaction.
• the neutral glycerol containing catalyst or compounds derived from the catalyst is neutralized by an acid such as for example hydrochloric acid or sulfuric acid
• the neutral glycerol will contain salts such as for example sodium or potassium chlorides or sodium or potassium sulfates.
• a treatment to eliminate them must be inserted between this step and the final step of incorporating the glycerol ether derivative or the acetal glycerol derivative in the fuel.
• This treatment generally consists of a distillation of the prepared product, which is costly in investment and in energy.
• the invention provides a process for manufacturing a composition which can be used as fuel or as fuel constituent from '' at least one triglyceride formed between at least one fatty acid and glycerol, said process comprising: - at least one transesterification step in which said triglyceride is reacted by heterogeneous catalysis with at least one primary monoalcohol chosen from methanol and ethanol, to give, on the one hand, at least one methyl and / or ethyl ester of the fatty acid (s) of the starting triglyceride (s) and, on the other hand, of glycerol, these products being free from by-products; and - an etherification step in which the glycerol is reacted with at least one olefinic hydrocarbon of 4 to 12 carbon atoms; and / or - an acetalization step in which the glycerol is reacted with at least one compound chosen from aldehydes, ketones and ace
• catalysis Two types of catalysis can be envisaged for carrying out the transesterification of a vegetable oil into methyl (or ethyl esters) from heterogeneous catalysts: catalysis in a batch reactor or continuous catalysis using the principle of the fixed bed. Generally, we work continuously in a fixed bed.
• any solid catalyst operating in heterogeneous mode can be used, chosen in particular from: - those which comprise at least one oxide of at least one element chosen from groups IIB (by example Zn), IVA (for example Ti or Zr) and VB (for example Sb or Bi) of the Periodic Table; - those which comprise a mixture of at least aluminum oxide with at least one other oxide of at least one element chosen from groups IIB, IVA and VB; and - those which comprise at least one mixed oxide formed between aluminum oxide and at least one other oxide of at least one element chosen from the groups MB, IVA and VB.
• the catalyst can more particularly comprise: a mixture of zinc oxide and alumina or a zinc aluminate, for example of the spinel type, corresponding to the formula: ZnAl2 ⁇ 4, x1 ZnO, y1 AI2O3 (x1 and y1 being each between 0 and 2); - titanium oxide or a mixture of titanium oxide and alumina corresponding to the formula: (TiO ⁇ 2) y2 (Al2 ⁇ 3) i-y2 (x2 having a value of 1.5 to 2.2 and y2, representing the mass ratio of the two oxides, having a value of 0.005 to 1); - zirconium oxide or a mixture of zirconium oxide and alumina corresponding to the formula: (x2 having a value of 1.5 to 2.2 and y2, representing the mass ratio of the two oxides, having a value of 0.005 to 1); - a mixture of antimony and alumina oxide corresponding to the formula: (SbO ⁇ 3) y3 (Al2 ⁇ 3)
• the catalyst can be in the form of extrudates with a diameter of between 0.5 and 3 mm and is packaged in a tube making it possible to operate in a fixed bed.
• the diameter of the reactor must be adapted to the desired hourly production, all of which can be heated and withstand the pressure.
• This type of catalyst it is possible, for example, to operate in the following manner, in one or more stages.
• the case of the preparation of methyl esters is illustrated. Vegetable oil and methanol are introduced in an updraft into a reactor preheated to a temperature which may be between 170 and 250 ° C. and preferably between 190 and 210 ° C., at operating pressures between 3 and 6 MPa.
• VVH oil volume / catalyst volume / hour
• alcohol / oil weight ratio varying from 2/1 to 0.1 / 1.
• the catalyst is not found in the ester or in the glycerol.
• No neutralization or washing operation is required to remove the catalyst or a compound derived from the catalyst.
• the glycerol thus obtained has a purity at least equal to 98%. It does not contain metals, no neutralizing salts and its water concentration is limited by those of the starting materials used in the manufacture of Biodiesel, that is to say oil and monoalcohol.
• the glycerol obtained can be used directly in an etherification reaction with isobutene in the presence of an acid catalyst according to a technology well known to those skilled in the art, without prior treatment of this glycerol.
• This reaction is described for example in US-A-1,968,033.
• the composition of the mixture obtained can be changed, either by modifying the glycerol / olefin ratio (for example isobutene ), or by varying the residence time of the mixture on the catalyst.
• the hydrocarbon-soluble glycerol derivative thus obtained (glycerol ether) may be incorporated into a fuel of the diesel, Biodiesel or petrol type.
• glycerol ethers can be introduced into diesel fuels at a concentration such that they are soluble in said fuels. Depending on the case, proportions of 1 to 40% by volume are used, most often from 1 to 20% by volume.
• concentration of glycerol ethers in gasolines can range, for example, up to 50% by volume.
• the process of the invention can be represented by the following diagram: triglyceride methyl esters -> or ethyl oil S (biodiesel conventional inel) > new biodiesel t-butyl ethers meina ⁇ oi J. Ac ⁇ l) glycerol or isobutene ethanol diesel or petrol formulations
• the new Biodiesel thus obtained can, for its part, be used pure or as a mixture in gas oil and the mixture of tertiobutyl glycerol ethers obtained can be incorporated in a gas oil alone or in a gas oil already containing Biodiesel or in a fuel of petrol type. In this scheme, all of the initial triglyceride is used as fuel.
• This new Biodiesel can be used as is in a diesel engine or mixed in all proportions with diesel and or a conventional Biodiesel fuel ester. In this scheme, all of the initial triglyceride is used as fuel.
• the glycerol ethers obtained by the manufacturing process according to the invention can also find other applications, for example as solvents, surfactants or co-surfactants.
• the glycerol obtained at the end of the transesterification step or steps can also be used directly in an acetalization reaction with an aldehyde or a ketone or an acetal derived from such an aldehyde or from such a ketone, in particular presence of an acid catalyst according to a technology well known to those skilled in the art, and this without prior treatment of this glycerol.
• Acetalization reactions are described for example in the following documents: J. Gelas: Bulletin Soc. Chimique de France, 1969, n ° 4, 1300; J. Gelas: Bulletin Soc. Chimique de France, 1970, n ° 6, 2341; A J. shower et al: Chem.
• glycerol acetal may be incorporated into a fuel of the diesel, Biodiesel or petrol type.
• glycerol acetals can be introduced into diesel fuels at a concentration such that they are soluble in said fuels. Depending on the case, proportions of 1 to 40% by volume are used, most often from 1 to 20% by volume.
• the process of the invention can be represented by the following diagram: methyl esters triglycerides -, or ethyl oils (biodiesel convention nel) new biodiesel methanol acetals or ethanol glycerol D. aango. II o formulations with diesel or petrol
• the new Biodiesel thus obtained can, for its part, be used pure or as a mixture in gas oil and the glycerol acetal obtained can be incorporated in a gas oil alone or in a gas oil already containing Biodiesel or in a fuel of gasoline type. . In this scheme too, all of the initial triglyceride is used as fuel.
• glycerol obtained by transesterification of a rapeseed oil with methanol was acetalized with acetone to obtain 2,2-dimethyl-1, 3-dioxolane-4-methanol, also sometimes called solketal, and if all of this acetal were incorporated into all of the methyl ester of rapeseed oil obtained, a new Biodiesel would be obtained whose composition would be close to 87.5% by mass of methyl ester of the oil rapeseed and 12.5% by mass of solketal.
• This new Biodiesel could be used as it is in a diesel engine or mixed in all proportions with diesel and or a conventional Biodiesel fuel ester.
• the glycerol acetals obtained by a manufacturing process according to the invention can also find other applications, for example as solvents, surfactants or co-surfactants. The following examples illustrate the invention without limiting its scope.
• Example 1 A rapeseed oil is transesterified with methanol according to a process using a heterogeneous catalyst consisting of zinc aluminate.
• a heterogeneous catalyst consisting of zinc aluminate.
• the pressure in the apparatus is maintained between 5 and 6 MPa.
• the reaction mixture is then evaporated so that the majority of the glycerol formed is removed by decantation.
• the supernatant fraction of the esters produced containing approximately 94% by weight of methyl esters is subjected to a second stage of catalysis under identical operating conditions.
• the product resulting from this second catalysis step is completely rid of the excess methanol it contains by a distillation step.
• a second minority fraction of glycerol is obtained by decantation and is mixed with that obtained at the end of the first stage of catalysis.
• the glycerol is then treated under vacuum to remove traces of methanol.
• the glycerol obtained will be used without additional treatment in the examples which follow.
• Examples 2 to 4 Synthesis of tert-butyl glycerol ethers
• Glycerol obtained according to Example 1 is introduced in its raw form - that is to say without purification or additional treatment - into an autoclave reactor equipped with a system of stirring is of a gas introduction system containing a catalyst consisting of an acid-type ion exchange resin, the Amberlyst 15® resin.
• the medium is brought with stirring to a temperature of 50 ° C., then a controlled amount of isobutene is introduced into the reactor. the temperature is maintained between 50 ° C and 90 ° C for 3 hours. After returning to ambient temperature, the excess of isobutene is removed, the catalyst is separated by filtration and any volatile compounds which may be present are eliminated by evaporation.
• a colorless liquid is obtained, which is a mixture of tert-butyl ethers of glycerol.
• Example 5 In a fixed bed reactor containing 50 ml of washed and dried Amberlyst 15® resin, glycerol obtained according to Example 1 and isobutene are introduced in a molar ratio 1 / 2.8 while maintaining a flow rate ensuring a residence time of 30 minutes at a temperature of 80 ° C and under a pressure of 1 MPa. At the outlet of the reactor, if necessary, the excess of isobutene is eliminated by expansion and, after evaporation of any oligomers of isobutene, a product is obtained whose composition is similar to that of the mixture obtained in Example 4 (see Table 1 above).
• Example 6 920 g (10 moles) of glycerol obtained as described in Example 1, 790.3 g (10.96 moles) of n-butyraldehyde and 24 g of an Amberlyst 15® acid resin are introduced into a reactor. The medium is brought to 54 ° C. with stirring for 7 hours, during which 120 g of n-butyraldehyde are introduced.
• the reaction is as follows:
• Example 8 A fixed bed reactor containing 50 cm3 of an Amberlyst 15® resin is fed with glycerol obtained as described in Example 1 and acetone in an acetone / glycerol molar ratio of 1.2 / 1. The flow rate of the two reagents is adjusted so that the residence time is 30 minutes. The temperature in the reactor is brought to 80 ° C and the pressure is kept at 5 bar (0.5 MPa). At the outlet of the reactor, the medium is subjected to an expansion, then the residual acetone as well as the water coming from the reaction are eliminated by evaporation under reduced pressure.
• the liquid product collected is introduced into a second fixed bed reactor identical to the first, also supplied with acetone according to an acetone / effluent mass ratio of the first reactor 50/100.
• the reaction in this second reactor is carried out under the same conditions as those described for the first.
• the medium is subjected to an expansion, then the residual acetone as well as the water coming from the reaction are eliminated by evaporation under reduced pressure.
• the liquid product collected has the same characteristics as that obtained in Example 7.

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• 2005
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