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WO2018173011A1 - Catalyseurs hétérogènes, leur processus de préparation et leur application dans un processus de production d'esters alkyliques d'acides gras - Google Patents

Catalyseurs hétérogènes, leur processus de préparation et leur application dans un processus de production d'esters alkyliques d'acides gras Download PDF

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WO2018173011A1
WO2018173011A1 PCT/IB2018/052027 IB2018052027W WO2018173011A1 WO 2018173011 A1 WO2018173011 A1 WO 2018173011A1 IB 2018052027 W IB2018052027 W IB 2018052027W WO 2018173011 A1 WO2018173011 A1 WO 2018173011A1
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Prior art keywords
oxides
aluminium
silicon
catalysts
aluminosilicates
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PCT/IB2018/052027
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English (en)
Inventor
Andreia Filipa RIBEIRO DE OLIVEIRA PEIXOTO
Ana Cristina MOREIRA FREIRE
Sónia Isabel MATOS SILVA
Paula Cristina TEIXEIRA DA COSTA
Carlos Alberto DUARTE SOUSA
Bruno Miguel MAGALHÃES JARRAIS
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Universidade Do Porto
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • 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
    • 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
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • 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

Definitions

  • the present application refers to the technical field of heterogeneous (acid) catalysts, the production thereof and the application thereof in fatty acid alkyl esters production .
  • Biodiesel is a clean, biodegradable renewable fuel and was recently considered one of the best candidates for replacing fossil fuels.
  • the greatest obstacle against its commercialization compared with oil-derived fuels, relates to high production costs.
  • biodiesel a feasible alternative for diesel-derivatives production, especially for countries dependent on foreign oil supplies.
  • the world production of biofuels is forecast to increase at an average of 4% per year up to 2030, despite the impact of economic recession in some countries investing on the development of biofuels.
  • biodiesel is generally considered a viable "green” fuel that reduces harmful gas emissions
  • demand for these biofuels may have a very strong impact on the global agricultural market and on the price of food.
  • the first-generation biodiesel (conventional) is typically produced from oilseed crops (plants containing high oil content, such as soybean, palm, colza/canola, etc.) .
  • Transesterification is the process whereby the triacylglycerols present in the fats or oils react with an alcohol in the presence of a catalyst to form esters and glycerol.
  • the conventional processes used for the commercial production of biodiesel are catalysed by bases in homogeneous phase, which though resulting in high conversion percentages of triacylglycerols into FAAE (biodiesel) in a short reaction time, has several drawbacks. Firstly, it requires various steps: esters purification, glycerol separation ( another products from transesterification reaction) , complicated separation processes for removing the catalyst, limitations of the raw materials quality, with FFA contents not exceeding 2%, to prevent saponification side reactions occurring simultaneously with consequent decrease in catalytic activity of the catalyst.
  • liquid acids as catalysts has a big disadvantage in this type of transesterification reactions when compared to alkalines, namely that water produced in the esterification of the FFA inhibits the transesterification of triacylglycerols.
  • Another big disadvantage is the fact that these liquid acids possess highly corrosive character which causes problems of process machinery deterioration significantly increasing the maintenance costs.
  • the process of acid catalysis is used to minimize the high content FFA raw materials contaminations
  • heterogeneous catalysts such as solid acid and bases and enzymes may overcome most of the problems associated to the use of processes using homogeneous catalysts and it is in this sense that there is a growing interest to replace the homogeneous conventional catalysts for heterogeneous catalysts (solids) .
  • the catalysts prepared and described in this patent application solve the operating problems associated to the use of homogeneous catalysts.
  • the solid acid catalysts (of the Lewis type, such as mixtures of oxides, and of the Br0nsted type, such as materials containing acid groups or intrinsic acidity) combine the advantages of the heterogeneous catalysts with those of the mineral acids (liquid) enabling simultaneous esterification and transesteri fication of the raw materials.
  • Another particular advantage of this class of catalysts is their efficiency in transforming raw materials rich in high-FFA contents into biodiesel, assuring the use of low-cost and easily-obtainable raw materials without the need of pre-treatment steps.
  • the steps of neutralization and catalyst elimination are avoided.
  • the solid catalysts are easily handled and regenerated, are selective and reused, and the problems of corrosion are minimized or even surpassed and are applicable in continuous flow processes.
  • Patent document US7122688 B2 [28] describes a method to prepare alkyl esters from palmitic acid (PA) and soybean oil enriched with PA.
  • the catalyst is mesoporous silica functionalized with sulfonic acids (alkyl and aryl) .
  • the functionalized mesoporous silica presents a low number of acid centres (0.60 -1.44 mmol H + /g mate riai ) when compared to the catalysts prepared and described in the present patent application, which limits their acid catalytic efficiency and their reuse. Conversions to the palmitic acid in the respective methyl palmitate are high (% AP ⁇ 3), though no raw materials with high FFA content (%) were tested.
  • Patent document US20120130101 Al [29] describes the preparation and use of ceramic catalysts for preparing free fatty acid alkyl esters.
  • the solid catalyst was obtained by mixing and sintering 0-80 wt . % active catalyst (metal oxides, carbonates or hydroxides) with a support material which is a mixture of silica and aluminium oxides.
  • active catalyst metal oxides, carbonates or hydroxides
  • the materials prepared were used in the transesterification and esterification of vegetable and animal oils using high temperatures between 150-250°C and 120-250°C, respectively.
  • the conversions obtained were superior to 90%, however the pressure and temperature conditions used are much higher than those used with the catalysts prepared and described in the present patent application.
  • Patent document MX2011012089 [30] describes an industrial process to obtain a mixture of FAME by esterification and transesterification of triacylglycerol using bentonite-type clay as catalyst. This clay was treated with water and with trifluoromethanesulfonic acid, the clay acts as support for the strong homogeneous acid catalyst.
  • the acidity value of the materials prepared is not described, nor the results obtained in the transesterification and esterification processes of vegetable oils and animal fat.
  • the process involves various pre-treatment steps of the raw materials, making it economically unfeasible for industrial application; there is no need of raw material pre-treatment with catalysts prepared and described in the present patent application .
  • Patent document WO2009016646 Al[31] describes a glycerol- based heterogeneous solid acid catalyst employed for the esterification of fatty acids.
  • the catalyst is prepared with large quantities of concentrated sulfuric acid and at high temperatures of 200 and 300°C, which makes the process of producing the catalyst costly in energy terms.
  • the catalysts display high acidity indices of 1.6-4.6 mmol H + /g ma teriai A but lower than some of the examples described in the present patent application displaying superacid characteristics (up to 6.0 mmol H + /g mate riai) ⁇
  • Patent document US8314045 Bl describes the preparation of an acid catalyst with a porous silica support and a sulfonated carbon layer disposed within the pores of the silica support. Moreover, it discloses esterification methods of free fatty acids using different types of solid catalysts such as ion exchange resins [33], strongly acidic cationic exchange resins followed by strongly basic anionic exchange resins [34] .
  • the main problem of ion exchange resins relates to their sensitivity to impurities such as metal ions, with a strong likelihood of becoming deactivated and, for this reason, there is a need of raw material pre-treatment , which is not is not necessary with the catalysts prepared and described in the present patent application whose raw materials are used directly without any prior treatment and no deactivation of catalyst is noted at all.
  • Patent document [35] US9328054 Bl of 2016 refers to a process that uses alcohol in a counterflow vapour-phase, a heterogeneous catalyst and in some embodiments, pressures lower than supercritical pressures for producing fatty acid esters.
  • the reactors are superheated to temperatures between 200-260°C, meaning the processes are unfavourable in energy terms.
  • the catalysts of the present patent application do not require high temperatures ( ⁇ 120°C) , nor pressures near supercritical pressures to obtain conversions into FAAEs near or equal to 100%, which demonstrates its catalytic efficiency.
  • the present application describes heterogeneous acid catalysts (solids) based on mixtures of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having different Al/Si ratios and respective preparation method.
  • said heterogeneous catalysts comprise: a mixture of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having the base formula selected from (Na, Ca) 0.33 (Al,Mg) 2 (Si 4 Oio) ( ⁇ ) 2 . ⁇ 2 0 or Al 2 Si 2 0 5 (OH) 4 . ⁇ 3 ⁇ 40 or Nao.33 (Al,Mg) 2 (S1 4 O 10 ) ( ⁇ ) 2 . ⁇ 2 0, wherein n represents the number of 3 ⁇ 40 molecules;
  • an organosilane selected from benzyltriethoxysilane, benzyltrichlorosilane, 4-biphenyliltriethoxysilane, 2- (4- chlorosulfonylphenyl ) ethyltrichlorosilane, 2- (4- chlorosulfonylphenyl ) ethyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3- mercaptopropyltrimethoxysilane, 1- (naphthylmethyl ) trichlorosilane, 1- (naphthylmethyl ) triethoxysilane, 1- (naphthylmethyl ) trimethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenyltrimethoxysilane phenethyltrichlorosilane, phenethyltri
  • the heterogeneous catalysts comprise: a mixture of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having the base formula selected from (Na, Ca) 0.33 (Al,Mg) 2 (S14O10) ( ⁇ ) 2 . ⁇ 2 0 or Al 2 Si 2 0 5 (OH) 4 . ⁇ 2 0 or Nao.33 (Al,Mg) 2 (S14O10) ( ⁇ ) 2 . ⁇ 2 0, wherein n represents the number of H 2 0 molecules;
  • the heterogeneous catalysts comprise: a mixture of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having the base formula selected from (Na, Ca) 0.33 (Al,Mg) 2 ( S 14O10 ) ( ⁇ ) 2 . ⁇ 2 0 or Al 2 Si 2 0 5 (OH) 4 . ⁇ 2 0 or Nao.33 (Al,Mg) 2 ( S 14O10 ) (OH) 2 .-nH 2 0, wherein n represents the number of H 2 0 molecules; and,
  • an organic precursor selected from fluoro-alkyl-sultones , alkyl-sultones , benzyl alcohol and organosulfonates ;
  • the catalysts comprising a mixture of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having base formula (Na, Ca) 0.33 (Al,Mg) 2 (Si 4 Oi 0 ) (OH) 2 .
  • nU 2 present a surface area between 200 and 300 m 2 /g and an acidity between 0.4 to 6.0 mmol H + /g mate riai ⁇
  • the catalysts comprising a mixture of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having base formula AI 2 S1 2 O 5 (OH) 4 .
  • ⁇ 2 0 present a surface area between 50 and 150 m 2 /g, and an acidity between 0.6 and 3.0 mmol H + g mate riai ⁇
  • the catalysts comprising a mixture of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having base formula Nao. 33 (Al,Mg) 2 (Si 4 Oi 0 ) ( ⁇ ) 2 . ⁇ 2 0 present a surface area between 50 and 100 m 2 /g, and an acidity between 2.0 and 5.0 mmol H + /g mate riai ⁇
  • Al/Si aluminium/silicon
  • aluminosilicate selected from (Na, Ca) 0.33 (Al,Mg) 2 (Si 4 Oi 0 ) (OH) 2 . ⁇ 2 0 or Al 2 Si 2 0 5 (OH) 4 . nE 2 0 or Nao.33 (Al,Mg) 2 (S14O10) (OH) 2 .
  • ⁇ 2 0, and an organosilane selected from benzyltriethoxysilane, benzyltrichlorosilane, 4-biphenyliltriethoxysilane, 2- (4- chlorosulfonylphenyl ) ethyltrichlorosilane, 2- (4- chlorosulfonylphenyl ) ethyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3- mercaptopropyltrimethoxysilane, 1-
  • oxidants selected from hydrogen peroxide (H 2 O 2 ) , nitric acid (HNO 3 ) , potassium permanganate
  • the method of preparing heterogeneous catalysts as described in the prior embodiment additionally comprises an acid activation step with a mineral acid selected from sulfuric (H 2 S0 4 ) , phosphoric (H 3 PO 4 ) , hydrofluoric (HF) , nitric (HNO 3 ) , hydrochloric (HC1), chlorosulfonic (HSO 3 CI) and acetic (CH 3 CO 2 H) acids.
  • a mineral acid selected from sulfuric (H 2 S0 4 ) , phosphoric (H 3 PO 4 ) , hydrofluoric (HF) , nitric (HNO 3 ) , hydrochloric (HC1), chlorosulfonic (HSO 3 CI) and acetic (CH 3 CO 2 H) acids.
  • Al/Si aluminium/silicon
  • aluminosilicate selected from (Na, Ca) 0.33 (Al,Mg) 2 (Si 4 Oi 0 ) (OH) 2 . nE 2 0 or Al 2 Si 2 0 5 (OH) 4.
  • a mineral acid selected from sulfuric (H 2 SO 4 ) , phosphoric (H 3 PO 4 ) , hydrofluoric (HF) , nitric (HNO 3 ) , hydrochloric (HC1), chlorosulfonic (HSO 3 CI) and acetic (CH 3 CO 2 H) acids.
  • Al/Si aluminium/silicon
  • aluminosilicate selected from (Na, Ca) 0.33 (Al,Mg) 2 (S14O10) ( ⁇ ) 2 . ⁇ 2 0 or Al 2 Si 2 0 5 (OH) 4 . ⁇ 2 0 or Nao.
  • Al/Si aluminium/silicon
  • aluminosilicate selected from (Na, Ca) 0.33 (Al,Mg) 2 (S14O10) ( ⁇ ) 2 . ⁇ 2 0 or Al 2 Si 2 0 5 (OH) 4 . ⁇ 2 0 or Nao.33 (Al,Mg) 2 (S14O10) (OH) 2 .-nH 2 0, and an organic precursor selected from fluoro-alkyl-sultones , alkyl-sultones , benzyl alcohol and organosulfonates .
  • the method of preparing heterogeneous catalysts as defined in the preceding embodiment additionally comprises an acid activation step with a mineral acid selected from sulfuric (H 2 SO 4 ) , phosphoric (H 3 PO 4 ) , hydrofluoric (HF) , nitric (HNO 3 ) , hydrochloric (HC1), chlorosulfonic (HS0 3 C1) and acetic (CH 3 C0 2 H) acids.
  • a mineral acid selected from sulfuric (H 2 SO 4 ) , phosphoric (H 3 PO 4 ) , hydrofluoric (HF) , nitric (HNO 3 ) , hydrochloric (HC1), chlorosulfonic (HS0 3 C1) and acetic (CH 3 C0 2 H) acids.
  • a silylation reaction occurs in a non- hydrolytic solvent, carried out under inert atmosphere, at a temperature between 50 - 140°C, with stirring in a period between 2-24 hours.
  • a silylation reaction is carried out at a temperature of 120°C for 6 hours.
  • the catalysts are separated from the reaction medium by centrifugation and/or filtration.
  • heterogeneous catalysts as defined in this patent application are used in the production of fatty acid alkyl esters, by esterification and/or transesterification of free fatty acids and/or triacylglycerols and mixtures thereof and/or in catalytic reactions of hydrotreatment , condensation, alkylation, isomerization, dehydration, opening of epoxides, hydrolysis or aldol reactions.
  • the present application describes heterogeneous catalysts (solids) based on mixtures of aluminium/silicon (Al/Si) oxides and/or aluminosilicates having different Al/Si ratios and respective preparation method.
  • the catalysts described herein are designated by X-CAT(1-12), Y-CAT(1-12) and Z-CAT(1-12) .
  • the present technology is not limited to heterogeneous acid catalysts and the preparation thereof, but also includes their application in the esterification of free fatty acids (FFA) and transesterification of triacylglycerols (TG) for producing fatty acid alkyl esters
  • FAAE FFAAE and includes the process and technology for obtaining them, using traditional and alternative raw materials, vegetable oils and animal fats with FFA percentages from 0 to 100%.
  • the present patent application also describes a simple process of transforming different types of raw materials of vegetable origin, animal origin, and residues thereof, residues from forest and agricultural biomass (ligno- cellulosic) and the processing thereof, non-edible crops
  • GSG GHG
  • ILUC indirect land use change
  • the catalysts described herein and designated by X-CAT(1-12), Y-CAT(1-12) and Z-CAT(1-12), display excellent activity as heterogeneous catalysts acids for producing FAAE associated to a simplified industrial process.
  • the application of the methodology of preparing the heterogeneous catalysts, which the present patent application constitutes, is not limited to the production of FAAE from esterification and transesterification reactions, but may still be used in catalytic reactions of hydrotreatment , condensation, alkylation, isomerization, dehydration, opening of epoxides, hydrolysis, aldol reactions, but is not limited thereto.
  • the present technology also constitute an alternative to conventional and outdated processes of producing FAAE using liquid inorganic acids and are associated to high expenses with maintenance and waste water treatment.
  • These processes also have the additional disadvantage of not being efficient in transforming raw materials rich in FFA (up to 100% of FFA) and, consequently, oblige the need to adapt and/or alter the conventional processes for alternative processes which includes that described by the present patent application and which enable efficient and clean production of FAAE from any type of raw material.
  • the catalysts prepared and described in this patent application and used in the production of FAAE enable realization conditions such as: pressures of 1 to 20 atm, temperatures between 60 and 160°C, batch or continuous reactions; in the transesteri fication reaction and/or esterification of free fatty acids such as, but not limited to these, valeric, myristic, lauric, palmitic, palmitoleic, stearic, oleic, linoleic acids, or different percentages of mixtures of FFA or mixtures of FFA with TG (but not limited to these) which present conversions of 100% in some of the examples of embodiments.
  • heterogeneous catalysts prepared and described in this patent application enable the use of any type of raw material comprised of free fatty acids (0 to 100%) and/or triacylglycerols including the transformation of residues of any type and quality having high amounts of FFA (up to 100%), water and other impurities, in FAAE, having reaction times of 30 to 240 min, in one step or in 2 or 3 steps, with raw material : alcohol ratio of 1:1 to 1:60, and catalyst mass percentages of 2 to 10%.
  • the use of heterogeneous catalysts prepared and described in this patent application enables all type of raw materials, including residues of animal or vegetable origin with no need of pre-treatment with the advantage of catalyst reusability from 2 to 20 times without loss of activity.
  • FIGURE 1 Representative layout of the catalysts prepared and described in this patent application, X-CAT(1-12), Y- CAT(1-12) and Z-CAT ( 1-12 ) ) .
  • the catalysts of the present technology and described herein are based on a mixture of oxides of (Al/Si) and/or aluminosilicates of the type
  • the catalysts produced from oxides Al/Si and/or aluminosilicates X-AISi, Y-AISi and Z-AISi will be designated by X-CAT(1-12), Y-CAT(1-12) and Z-CAT(1-12), respectively, wherein (1-12) they merely serve to identify the different catalysts (described herein for illustration) within each class (X, Y or Z) based on their method of production.
  • the catalysts prepared present superacid characteristics (0.4 to 6.0 mmol H + /g ma teriai) and surface areas between 50 and 300 m 2 /g.
  • the catalysts X-CAT have surface areas between 200-300 m 2 /g and an acidity from 0.4 to 6.0 mmol HV g t starting material ) , wherein X-CAT 1 and X-CAT 12 have an acidity of 0 . 4 , X - CAT 4 and X-CAT 9 of 0 . 7 , X-CAT 6 and X- CAT 1 0 of 6 . 0 and X-CAT 1 1 of 3 . 0 mmol H + / g mate riai .
  • the catalysts Y-CAT has a surface area of 50-150 m 2 /g, acidity from 0.6 to 3.0 mmol
  • Y-CAT1 has an acidity of 0.6, Y-CAT 6 of 3.0 and Y-CAT10 of 2.0 mmol H + /g material .
  • the catalysts Z-CAT have a surface area of 50-100 m 2 /g, an acidity from 2.0 to 5.0 mmol H + /g ma teriai A wherein Z-CAT10 has an acidity of 2.0 and Z- CAT11 of 5.0 mmol H + /g mate riai .
  • the heterogeneous catalysts are prepared by silylation reaction with silylation agents of the organosilane type with different hydrolysable groups: ethoxy-, methoxy- and chloro-, and different functional groups phenyl-, benzyl-, naphthyl- biphenyl-, mercapto-, chlorosulfonyl-, selected from, but not limited to, benzyltriethoxysilane, benzyltrichlorosilane, 4 - biphenyliltriethoxysilane, 2- ( 4 - chlorosulfonylphenyl ) ethyltrichlorosilane, 2- ( 4 - chlorosulfonylphenyl ) ethyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3- mercaptopropyltrimethoxysilane, 1- (naphthylmethyl ) t
  • the organosilane mercaptopropyltrimethoxysilane is designated ORG-1
  • the phenyltrimethoxysilane designated ORG-2
  • the phenyltriethoxysilane is designated ORG-3
  • the 2- (4- chlorosulfonylphenyl ) ethyltrimethoxysilane is designated ORG-4, in this patent application.
  • ORG1 the intermediate products that underwent the silylation process but which do not yet have catalyst activity, have the suffix ORG1, ORG2, ORG3 or ORG4, depending on the organosilane used to obtain it (e.g. X-AlSi-ORGl, Y-AlSi-ORG3, etc.) .
  • the silanol reactive group formed condenses with the reactive groups present in the mixture of Al/Si oxides and/or aluminosilicates of the type
  • a silylation reaction is carried out under inert atmosphere (e.g. nitrogen), using temperatures between 50 and 140°C, regular stirring periods varying between 2-24 hours.
  • inert atmosphere e.g. nitrogen
  • a silylation reaction is carried out at a temperature of 120°C for 6 hours.
  • the catalyst is prepared by silylation with the silylation agents ORG1, ORG2, ORG3 and ORG4 with different hydrolysable groups, alkoxy, acyloxy or halogens, followed by acid activation, with the following mineral acids, but not limited to, sulfuric (H 2 SO 4 ) , phosphoric ( H 3 PO4 ) , hydrofluoric (HF) , nitric (HNO 3 ) , hydrochloric (HC1), chlorosulfonic (HS0 3 C1) and acetic (CH 3 C0 2 H) .
  • the silylation agents ORG1, ORG2, ORG3 and ORG4 with different hydrolysable groups, alkoxy, acyloxy or halogens, followed by acid activation, with the following mineral acids, but not limited to, sulfuric (H 2 SO 4 ) , phosphoric ( H 3 PO4 ) , hydrofluoric (
  • the catalyst is prepared by the silylation reaction with mercapto- type silylation agents with different hydrolysable groups: alkoxy, acyloxy or halogens, including 3-mercaptopropyltrimethoxysilane, followed by an oxidation process.
  • the oxidation process may be made using the following oxidants or combination thereof, but not limited to, hydrogen peroxide (H 2 O 2 ) , nitric acid (HNO3) , potassium permanganate ( ⁇ 4 ) , potassium chromate (K ⁇ CrC ⁇ ) and sodium hypochlorite (NaCIO) .
  • the catalyst is prepared by silylation reaction with phenyl-, benzyl-, naphthyl- biphenyl-, mercapto- type silylation agents with different hydrolysable groups: alkoxy, acyloxy or halogens, including the silylation agents ORG1, ORG2 and ORG3, followed by acid treatment.
  • the acid treatment is performed with mineral acids of the, but not limited to, H 2 S0 4 , H3PO4 , HF, HN0 3 , HC1, HS O 3 C I , CH 3 CO 2 H and p-toluenosulfonic acid (C 7 H 7 SO 3 H) type .
  • the starting material, a mixture of Al/Si oxides and/or aluminosilicates of the type X-AISi, Y- AlSi and Z-AISi already displays Lewis and/or Br0nsted acid properties.
  • the catalyst is prepared by direct or indirect activation of the starting material, a mixture of Al/Si oxides and/or aluminosilicates of the type X-AlSi, Y- AlSi and Z-AlSi:
  • Direct activation is carried out by mineral acids or sulfonic organic acids such as H2 S O4 , H 3 PO4 , HF, HNO 3 , HC1, HSO 3 CI, CH 3 CO 2 H and C 7 H 7 SO 3 H, but this activation is not limited to these examples.
  • mineral acids or sulfonic organic acids such as H2 S O4 , H 3 PO4 , HF, HNO 3 , HC1, HSO 3 CI, CH 3 CO 2 H and C 7 H 7 SO 3 H, but this activation is not limited to these examples.
  • Indirect activation is performed by reaction of the base materials with Al/Si mixed oxides and/or aluminosilicates of the type X-AlSi, Y-AISi and Z-AISi with different precursors: fluoro-alkyl-sultones , alkyl-sultones , benzyl alcohol, organosulfonates and other derivatives, but not limited thereto.
  • Indirect activation may be followed by acid activation by mineral acids or sulfonic organic acids such as H2 S O4 , H3PO4 , HF, HN0 3 , HC1, HSO3CI, CH 3 C0 2 H and C7H7 S O 3 H , but this activation is not limited to these examples .
  • the catalysts of the present technology and described herein are easily separated from the reaction medium by centrifugation and/or filtration (in the case of the batch reactor), is easily recoverable and reusable.
  • the heterogeneous catalysts and methods described herein constitute an efficient process for fatty acid alkyl esters production (biodiesel and bioproducts) with high yields under mild pressure and temperature conditions.
  • the catalysts prepared and described herein were applied to a one-step process for methyl esters (FAME- fatty acid methyl ester) and ethyl esters fatty acids production from the esterification and/or transesterification reaction of free fatty acids such as, but not limited to valeric, myristic, lauric, palmitic, palmitoleic, stearic, oleic, linoleic acids, or different percentages of mixtures of FFA or mixtures of FFA with TG (but not limited thereto) .
  • FFA FFA, mixtures of FFA or mixtures of FFA with TG, react with the alcohol in the presence of a catalyst prepared according to the method described herein for producing fatty acid alkyl esters.
  • the alcohol used in this procedure is, but not limited to, methanol or ethanol.
  • the molar ratio of raw material (RM) : methanol/ethanol may vary from 1:0.5 to 1:60. In some embodiments, the conversion achieved 90 to 100%.
  • the methyl/ethyl esters fatty acids produced by the process described herein include, but are not limited to, valeric, myristic, lauric, palmitic, palmitoleic, stearic, oleic, linoleic acids, or mixtures thereof and/or mixtures of other FFA and mixtures of FFA with TG.
  • the conditions used for producing alkyl esters are a temperature of 120°C and a pressure of 8 bar.
  • the catalysts of the present technology and described herein are efficient in the reaction (with atomic efficiency in agreement with the second principle of green chemistry) of transesteri fication and esterification of pure vegetable oils (TG and FFA) , or other raw materials comprised of mixtures of FFA and TG, using mild conditions of temperature between 60-160°C and pressure of 1 to 20 atm.
  • the products obtained are fatty acid alkyl esters including but not limited to, methyl and ethyl esters fatty acid , and pure glycerol.
  • the catalysts described herein have an excellent catalytic efficiency in the esterification and transesterification of FFA, TG, mixtures of FFA and mixtures of FFA with TG. They display the advantages of the heterogeneous catalysts, and avoid the use of toxic and corrosive chemical products, contributing to simplify the conventional industrial processes with consequent increase of the industrial process economy. Furthermore, contrary to conventional catalysts, the heterogeneous catalysts of the present technology are very efficient for raw materials with high content of free fatty acids, water and other impurities. Therefore, there are no limitations in the quality and type of raw materials to be used with the catalysts of the present technology.
  • raw materials of animal and vegetable origin may be pure or result from the hydrolysis of vegetable oils and animal fats, vegetable or aquatic biomass, residues of waste oil and fats.
  • residues of waste oil include residues of oils and fats, by-products of oil processing/refinery plants, food processing plants, restaurants, households in general; residues of oils and fats resulting from the processing of oils and fats, such as margarines and modified fats; residues of oils and fats such as vegetable oils and fats used as lubrication oils, residues of oils and fats from the processing of edible oils; edible oils and fats from returned merchandise, such as defective products and expired products, oils and animal fats occurring in edible fish or meat processing.
  • the process for producing FAAE from FFA, mixtures of FFA and mixtures of FFA with TG (and all the raw materials containing FFA and TG) and alcohol, and a solid catalyst prepared and described by the methods comprised in this patent application is a heterogeneous process and the catalyst may be separated from the reaction liquid by separation techniques such as, but not limited to, centrifugation/decanting and filtration.
  • the catalyst may be used as a pulverized sample or as granules or extrusion moulded, pelletized, beaded and/or atomized.
  • the process described herein for producing alkyl esters of FFA, mixtures of FFA and mixtures of FFA with TG is a single-step process.
  • the process described herein avoids pre-treatment steps of raw materials, the steps of saponification, neutralization, elimination of the catalyst, etc. associated to the conventional processes.
  • the conventional liquid catalysts may require treatment with mineral acids and alkaline bases, increasing the separation costs of the catalyst and consequently the operating costs.
  • the catalysts described herein lead to processes having excellent cost-benefit ratio and sustainability .
  • the catalysts were prepared using the methods described in examples of procedures which are set out below. Some examples of the catalytic results are presented in Tables 1, 2 and 3.
  • FFA 100% FFA (mixture of acids: lauric, palmitic, stearic, oleic and linoleic) .
  • FFA 100% FFA (mixture of acids: lauric, palmitic, stearic , oleic and linoleic
  • RM1 82 % FFA and 18 £ TG.
  • FFA 100% FFA (mixture of acids: lauric, palmitic, stearic, oleic and linoleic) .
  • Catalysts preparation referred in the present patent application is based on different mixtures of Al/Si oxides and/or aluminosilicates of the type X-AlSi, Y-AlSi and Z- AlSi .
  • Example 1.1 The catalysts X-CAT1, Y-CAT1 or Z-CAT1 (see figure 1) were prepared using the functionalized materials X-AlSi-ORGl, Y-AlSi-ORGl or Z-AlSi-ORGl, by treatment with H 2 O 2 30% (v/v) (2.66 mol), for 24 hours, under stirring and at room temperature. After 12 hours of reaction, concentrated sulfuric acid (0.5 mL) was added and the reaction was maintained for a further 12 hours. Afterwards, the catalysts X-CAT1, Y-CAT1 or Z-CAT1 were isolated by filtration and/or centrifugation and dried overnight using an oven at 100-120°C. The catalysts X-CAT1 and Y-CAT1 display an acidity of 0.4 and 0.6 mmol H + /g mate riai, respectively .
  • Example 1.2 The catalysts X-CAT2, Y-CAT2 or Z-CAT2 (see figure 1) were prepared using the method described in example 1, with an additional procedure: the materials X- AlSi-ORGl, Y-AlSi-ORGl or Z-AlSi-ORGl were treated with an aqueous solution of nitric acid (0.56 mol) . The mixtures were stirred for 6 hours at room temperature. Subsequently, the catalysts X-CAT2, Y-CAT2 or Z-CAT2 were isolated by filtration and/or centrifugation and dried in an oven at 100-120°C.
  • Example 1.3 The catalysts X-CAT3, Y-CAT3 or Z-CAT3 (see figure 1) were prepared using the method described in example 1, followed by oxidative chlorination with H 2 O 2 - SOCI2, using S0C1 2 (8 mmol) and H 2 0 2 30% (v/v) (24 mmol), in 20 mL of CH 3 CN at 25°C and stirring for 1 hour. The solids were removed by filtration and/or centrifugation, washed once with CH 3 CN and dried overnight at 100-120°C.
  • Example 1.4 The catalysts X-CAT4, Y-CAT4 or Z-CAT4 (see figure 1) were prepared using the method described in example 1, with an additional procedure: The functionalized materials X-AlSi-ORGl, Y-AlSi-ORGl or Z-AlSi-ORGl (2 g) were dispersed in CHCI 3 (25 mL) and transformed, subsequently, by dropwise addition of chlorosulfonic acid (9 mmol) .
  • the catalysts obtained, X-CAT4, Y-CAT4 or Z-CAT4 were washed with methanol, isolated by filtration and/or centrifugation and dried at 100-120°C.
  • the catalyst X-CAT4 displays an acidity of 0.7 mmol
  • silylation agents ORG2 with phenylmethoxy-functional group, 4.99 mmol
  • Example 2.1 The functionalized materials X-AlSi-ORG2, Y- AlSi-ORG2 or Z-AlSi-ORG2 and X-AlSi-ORG3, Y-AlSi-ORG3 or Z- AlSi-ORG3, obtained in example 2, were used as base for preparing the catalysts X-CAT5 , Y-CAT5 or Z-CAT5 and X- CAT7, Y-CAT7 or Z-CAT7 (see figure 1), by suspension in anhydrous diethyl ether (50 mL) and subsequent addition of 6 mL of sulfuric acid (5 M) . The mixture was stirred for 1 hour at ambient temperature.
  • the solid was separated by filtration and/or centrifugation and washed with water, up to pH ⁇ 7.
  • the catalysts X- CAT5, Y-CAT5 or Z-CAT5 and X-CAT7, Y-CAT7 or Z-CAT7 were recovered by filtration and/or centrifugation and dried at 100-120°C.
  • Example 2.2 The catalysts X-CAT6, Y-CAT6 or Z-CAT 6 and X- CAT8, Y-CAT8 or Z-CAT8 were prepared from the functionalized materials X-AlSi-ORG2, Y-AlSi-ORG2 or Z- AlSi-ORG2 and X-AlSi-ORG3, Y-AlSi-ORG3 or Z-AlSi-ORG3 (described in example 2, see figure 1), by dispersion in dichloromethane or other non-hydrolytic solvent (40 mL) and subsequent addition of chlorosulfonic acid (3.7 x lCr 2 mol) . The reaction was maintained in reflux and stirred for 6 hours.
  • X-CAT6, Y-CAT6 or Z-CAT 6 and X-CAT8, Y-CAT8 or Z-CAT8 were prepared from the functionalized materials X-AlSi-ORG2, Y-AlSi-ORG2 or Z- AlSi-ORG
  • the catalysts X-CAT 6 , Y-CAT6 or Z-CAT 6 and X-CAT8, Y-CAT8 or Z-CAT8 were separated and washed several times with dichloromethane. Finally, the catalysts were filtered and/or centrifuged and dried in an oven at 100-120°C.
  • the catalyst X-CAT6 displays an acidity of 3.0 mmol H + /g mate riai .
  • the catalyst X-CAT9 displays an acidity of 0.7 mmol
  • Example 4 The catalysts X-CAT10, Y-CAT10 or Z-CAT10 were obtained by direct activation with chlorosulfonic acid (3.0 x 10 ⁇ 2 mmol), in the presence of toluene or other non- hydrolytic solvent (40 mL) (see figure 1) . The mixture was kept at 0°C and, subsequently the chlorosulfonic acid was added dropwise. Afterwards, the mixture was stirred at ambient temperature for 5 hours. Finally, the catalysts X- CAT10, Y-CAT10 or Z-CAT10 were separated by filtration and/or centrifugation, washed several times with dichloromethane and dried at 100-120°C. The catalysts X- CAT10, Y-CAT10 and Z-CAT10 display an acidity of 6.0, 2.0 and 2.0 mmol H + /g mate riai respectively.
  • Example 5 X-CAT11, Y-CAT11 or Z-CAT11 (see figure 1) were prepared from the starting materials X-AlSi, Y-AlSi or Z- AlSi (2 g) by reaction of the starting materials X-AlSi, Y- AlSi or Z-AlSi with 1 , 2 , 2-trifluoro-2-hydroxy-l- trifluoromethyletane sulfonic ⁇ -sultone acid (4.34 mmol) in the presence of toluene or other non-hydrolytic solvent (80 mL) . The mixture was kept in reflux under magnetic stirring for 6 hours.
  • the catalysts X-CAT11, Y-CAT11, Z-CAT11 were filtered and washed several times with dichloromethane and dried in a oven at 100°C for 24 hours.
  • the catalysts X- CAT11 and Z-CAT11 display an acidity of 3.0 and 5.0 mmol H + /g mat eriai respectively.
  • Example 6 The catalysts X-CAT12 , Y-CAT12 or Z-CAT12 (see figure 1) were prepared directly by activation with mineral acid.
  • the catalyst X-CAT12 displays an acidity of 0.4 mmol H + /g mate ri a i respectively .
  • EA X-ray photoelectron spectroscopy
  • FTIR- ATR Fourier transformed infrared attenuated total reflectance
  • XRD X-ray diffraction
  • Example 7 The production of FAAE was tested using 6 types of different raw materials.
  • the mixture was heated to 120°C, under continuous stirring and under pressure (4-20 bar), in a batch reactor (500 mL) . After 60 to 180 minutes, the reaction mixture was cooled to room temperature.
  • the catalysts were separated from the reaction medium by filtration.
  • the following table presents the catalytic results obtained, which were monitored by gas chromatography with FID detection, HPLC and by 1 H RMN.
  • the catalysts of the present technology and described herein are based on a mixture of oxides of (Al/Si) and/or aluminosilicates of the type

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Abstract

La présente demande décrit des catalyseurs hétérogènes, également appelés catalyseurs acides solides, constitués de mélanges d'oxydes d'aluminium/silicium (A1/Si) et/ou d'aluminosilicates ayant des rapports A1/Si différents comprenant ceux du (Na, Ca) 0.33 (A1, Mg) 2 (Si4O10) (OH) 2.nE20, A12Si2O5 (OH) 4.nΗ2Ο, Na0.33 (A1, Mg) 2 (Si4O10) (OH) 2.type nΗ2Ο, mais sans y être limités, et des groupes acide sulfonique, ainsi que leurs procédés de préparation. La présente technologie comprend en outre l'application desdits catalyseurs hétérogènes dans les processus de production d'esters alkyliques d'acides gras FAAE par estérification d'acides gras libres (FFA) et transestérification de triacylglycérols (TG).
PCT/IB2018/052027 2017-03-24 2018-03-26 Catalyseurs hétérogènes, leur processus de préparation et leur application dans un processus de production d'esters alkyliques d'acides gras WO2018173011A1 (fr)

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