US20090235574A1 - Production of Bio-Diesel - Google Patents

Production of Bio-Diesel Download PDF

Info

Publication number
US20090235574A1
US20090235574A1 US11/908,313 US90831306A US2009235574A1 US 20090235574 A1 US20090235574 A1 US 20090235574A1 US 90831306 A US90831306 A US 90831306A US 2009235574 A1 US2009235574 A1 US 2009235574A1
Authority
US
United States
Prior art keywords
group
bas
cat
cation
neutral
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/908,313
Other languages
English (en)
Inventor
Martyn J. Earle
Kenneth R. Seddon
Natalia V. Plechkova
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of US20090235574A1 publication Critical patent/US20090235574A1/en
Abandoned legal-status Critical Current

Links

Images

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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
    • B01J31/0288—Phosphorus
    • 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
    • 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
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • 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
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method of producing bio-diesel, and, more specifically, to a method of producing bio-diesel using a stable ionic liquid as both solvent and catalyst.
  • Bio-diesel is the name given to a clean burning alternative fuel produced from domestic, and renewable, resources. Bio-diesel contains no petroleum, but can be blended at any level with petroleum diesel to create a bio-diesel blend. It can be used in compression-ignition (diesel) engines with little or no modifications. Bio-diesel is considered simple to use, biodegradable, non-toxic, and essentially free of sulfur and aromatics.
  • Bio-diesel is defined as mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats. Generally, Bio-diesel is made through transesterification of animal fat, wherein the glycerin is separated from the fatty acid methyl ester. Alternatively, it can be made through the esterification of vegetable oils, wherein the water byproduct is separated from the final fatty acid methyl ester.
  • Bio-diesel must be produced to strict industry specifications (ASTM D6751) in order to ensure proper performance and is the only alternative fuel to have fully completed the health effects testing requirements of the 1990 Clean Air Act Amendments. Bio-diesel that meets ASTM D6751 is registered with the Environmental Protection Agency as a legal motor fuel for sale and distribution.
  • the term “bio-diesel” refers to the pure fuel before blending with diesel fuel. Bio-diesel blends are denoted as, “BXX” with “XX” representing the percentage of bio-diesel contained in the blend (ie: B20 is 20% bio-diesel, 80% petroleum diesel).
  • Bio-diesel is environmentally friendly as it is made from renewable resources and has lower emissions compared to petroleum diesel. It is also less toxic than table salt and biodegrades as fast as sugar.
  • the acid catalysed esterification reaction is preferred, as water is the only by-product and this reaction occurs readily.
  • the base catalysed esterification to methyl or ethyl esters usually fails at normal temperatures and pressures, because the catalyst is inactivated by reaction with the carboxylic acid group (Scheme 1).
  • Enzymes have also been used with ionic liquids for vacuum-driven lipase-catalysed direct condensation of L-ascorbic acid and fatty acids in ionic liquids, i.e. synthesis of a natural surface active antioxidant.
  • the Brönsted acidic ionic liquid 1-methylimidazolium tetrafluoroborate has also been used for esterification.
  • [BF 4 ] ⁇ gives HF which is ultra corrosive, highly toxic and dissolves glass.
  • chymotrypsin-catalysed transesterification in ionic liquids and ionic liquid/supercritical carbon dioxide is also known.
  • Metallic Lewis acids-catalysed acetylation of alcohols with acetic anhydride and acetic acid in ionic liquids is also known.
  • transesterification/acylation reactions mediated by N-heterocyclic carbene catalysts are also known.
  • ionic liquid refers to a liquid that is capable of being produced by melting a solid, and when so produced, consists solely of ions. Ionic liquids may be derived from organic salts.
  • An ionic liquid may be formed from a homogeneous substance comprising one species of cation and one species of anion, or can be composed of more than one species of cation and/or anion.
  • an ionic liquid may be composed of more than one species of cation and one species of anion.
  • An ionic liquid may further be composed of one species of cation, and one or more species of anion.
  • the mixed salts of the invention can comprise mixed salts containing anions and cations.
  • ionic liquid may refer to a homogeneous composition consisting of a single salt (one cationic species and one anionic species) or it may refer to a heterogeneous composition containing more than one species of cation and/or more than one species of anion.
  • a class of ionic liquids which is of special interest is that of salt compositions with melting points below 100° C. Such compositions are mixtures of components which are often liquid at temperatures below the individual melting points of the components.
  • base refers to Brönsted bases having the ability to react with (neutralise) acids to form salts.
  • the pH range of bases is from 7.0 to 14.0 when dissolved or suspended in water.
  • the term “acid” refers to Brönsted acids having the ability to react with (neutralise) bases to form salts.
  • the pH range of acids is from 1.0 to 7.0 when dissolved or suspended in water.
  • the inventors of the present invention have surprisingly found that it is possible to produce bio-diesel using an ionic liquid which is stable to reaction conditions, thereby allowing continued recycling.
  • acid or base functionality can be incorporated into the ionic liquid to allow the ionic liquid to act as a catalyst and/or a solvent.
  • a method of obtaining bio-diesel comprising the step of esterifying or trans-esterifying fatty acids derived from plant or animal in the presence of a stable ionic liquid wherein the ionic liquid acts as both a solvent and a catalyst.
  • the ionic liquid is acidic or basic.
  • the ionic liquid may comprise a basic cation and a neutral anion, or a neutral cation and a basic anion, or both a basic cation and a basic anion, or mixture thereof.
  • the ionic liquid may comprise an acidic cation and a neutral anion, or a neutral cation and an acidic anion, or both an acidic cation and an acidic anion, or mixture thereof.
  • the basic cation preferably has the formula:
  • Bas preferably comprises at least one nitrogen, phosphorus, sulphur, oxygen or boron atom.
  • Bas comprises at least one primary, secondary or tertiary amino group.
  • Bas is selected from —N(R 1 )(R 2 ), and —P(R 1 )(R 2 ); and wherein R 1 and R 2 can be the same or different and are each selected from hydrogen, linear or branched alkyl, cycloalkyl, aryl and substituted aryl.
  • R 1 and R 2 are preferably each selected from hydrogen, methyl, ethyl, iso-propyl, butyl, sec-butyl, iso-butyl, pentyl, hexyl, cyclohexyl, benzyl and phenyl.
  • Bas is selected from —N(CH 3 ) 2 and —N(CH(CH 3 ) 2 ) 2 .
  • Z may be selected from linear or branched C 1 to C 18 alkanediyl, substituted alkanediyl, dialkanylether and dialkanylketone.
  • Z is selected from —(CH 2 —CH 2 )—, —(CH 2 —CH 2 —CH 2 )—, —(CH 2 —CH 2 —CH 2 —CH 2 )—, —(CH 2 —CH 2 —CH 2 —CH 2 )—, —(CH 2 CH 2 —CH 2 —CH 2 —CH 2 —CH 2 )—, —(CH 2 —CH 2 —O—CH 2 —CH 2 )— and —(CH 2 —CH 2 —O—CH 2 —CH 2 —CH 2 )—.
  • Cat + -Z-Bas may be selected from:
  • Cat + -Z-Bas is selected from:
  • Cat + -Z-Bas is selected from:
  • Cat+ may also comprise or consist of 1,3,5-trialkyl pyrazolium, 1,2-dialkylpyrazolium, and 1,2,3,5-tetraalkylpyrazolium.
  • Cat + -Z-Bas is selected from:
  • Cat + -Z-Bas may be selected from:
  • Cat + -Z-Bas may also be:
  • the basic anion has the formula [X b ] ⁇ , and may be selected from [F] ⁇ , [OH] ⁇ , [OR] ⁇ , [R—CO 2 ] ⁇ , [PO 4 ] 3 ⁇ and [SO 4 ] 2 ⁇ , wherein R is C 1 to C 6 alkyl.
  • [X b ] ⁇ is [OH] ⁇ .
  • the acidic cation preferably has the formula:
  • Acid is preferably selected from —SO 3 H, —CO 2 H, —SO 3 -Ph-R, —SO 3 R, RPO(OH)2 and R 2 PO(OH); wherein R is, for example, C 1 to C 6 alkyl.
  • [Cat + ] may comprise or consist of a heterocyclic ring structure selected from imidazolium, pyridinium, pyrazolium, thiazolium, isothiazolinium, azathiozolium, oxothiazolium, oxazinium, oxazolium, oxaborolium, dithiazolium, triazolium, selenozolium, oxaphospholium, pyrollium, borolium, furanium, thiophenium, phospholium, pentazolium, indolium, indolinium, oxazolium, isooxazolium, isotriazolium, tetrazolium, benzofuranium, dibenzofuranium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperazinium, piperidinium, morpholinium,
  • [Cat + ] may comprise or consist of a heterocyclic ring structure selected from pyridinium, pyrazolium, thiazolium, isothiazolinium, azathiozolium, oxothiazolium, oxazinium, oxazolium, oxaborolium, dithiazolium, triazolium, selenozolium, oxaphospholium, pyrollium, borolium, furanium, thiophenium, phospholium, pentazolium, indolium, indolinium, oxazolium, isooxazolium, isotriazolium, tetrazolium, benzofuranium, dibenzofuranium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperazinium, piperidinium, morpholinium, pyranium
  • [Cat + ] may comprise or consist of a heterocyclic ring structure selected from pyrazolium, isothiazolinium, tetrazolium, piperidinium, morpholinium and pyrrolidinium.
  • Cat + -Z-Acid is selected from:—
  • Cat + -Z-Acid is selected from:—
  • Cat + -Z-Acid is:
  • [X a ] ⁇ is selected from [HF 2 ] ⁇ , [HSO 4 ] ⁇ and [H 2 PO 4 ] ⁇ .
  • the neutral cation may comprise or consist of ammonium, phosphonium, pyrazolium, DBU or DBN.
  • the neutral cation is selected from:
  • the neutral cation is selected from:
  • the neutral cation is selected from:
  • the neutral cation may also comprise or consist of 1,3,5-trialkyl pyrazolium, 1,2-dialkylpyrazolium, or 1,2,3,5-tetraalkylpyrazolium.
  • the neutral cation is selected from:
  • neutral cation may be selected from:
  • the neutral cation may comprise or consist of a heterocyclic ring structure selected from imidazolium, pyridinium, pyrazolium, thiazolium, isothiazolinium, azathiozolium, oxothiazolium, oxazinium, oxazolium, oxaborolium, dithiazolium, triazolium, selenozolium, oxaphospholium, pyrollium, borolium, furanium, thiophenium, phospholium, pentazolium, indolium, indolinium, oxazolium, isooxazolium, isotriazolium, tetrazolium, benzofuranium, dibenzofuranium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperazinium, imidazolium, pyridinium
  • the neutral cation preferably comprises or consists of a heterocyclic ring structure selected from pyridinium, pyrazolium, thiazolium, isothiazolinium, azathiozolium, oxothiazolium, oxazinium, oxazolium, oxaborolium, dithiazolium, triazolium, selenozolium, oxaphospholium, pyrollium, borolium, furanium, thiophenium, phospholium, pentazolium, indolium, indolinium, oxazolium, isooxazolium, isotriazolium, tetrazolium, benzofuranium, dibenzofuranium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperazinium, piperidinium, piperidinium, piperidinium,
  • the neutral cation comprises or consists of a heterocyclic ring structure selected from pyridinium, pyrazolium, thiazolium, pyrimidinium, piperazinium, piperidinium, morpholinium, quinolinium, isoquinolinium and pyrrolidinium.
  • the neutral cation is selected from:—
  • the neutral cation is selected from:
  • the neutral anion may be a sulfonate, phoshinate, triflamide (amide), triflate, dicyanamide, oxide (phenoxide) or halide anionic species.
  • the neutral anion is selected from [C(CN) 3 ] ⁇ , [NTf 2 ] ⁇ , [OTf] ⁇ , [R—SO 3 ] ⁇ , [R 2 PO 2 ] ⁇ , [Cl] ⁇ , [Br] ⁇ and [I] ⁇ ; wherein R is C 1 to C 6 alkyl, or C 1 to C 6 aryl.
  • the neutral anion may also be selected from [Me-SO 3 ] ⁇ , [Ph-SO 3 ] ⁇ and [Me-Ph-SO 3 ] ⁇ .
  • the plant fatty acid may be derived from vegetables or cereal, for example, rape-seed oil, canola oil or prioline.
  • the ionic liquid will dissolve in solvents (reagents) such as methanol, water or ethanol, and remain separate from the bio-diesel phase. This allows the bio-diesel to be easily separated from the ionic liquid, and the ionic liquid phase can then be recycled.
  • solvents such as methanol, water or ethanol
  • FIG. 2 is a picture showing a separate methyl oleate (upper layer) product layer, wherein the left tube is before reaction (methanol/glycerol/[MIBS][OTf], and the right after reaction;
  • FIG. 3 is a proton NMR of Run 12 (54% conversion to methyl oleate) showing the glycerol ester peaks at 4.25 and 4.15 and the methyl oleate peak at 3.63 ppm;
  • FIG. 4 is a proton NMR of Run 1 (99% conversion to methyl oleate) showing the methyl oleate peak at 3.63 ppm and no glycerol ester peaks or ionic liquid peaks;
  • FIG. 5 is a proton NMR of Run 1 showing the methanol layer.
  • the ionic liquids used in the present invention may be produced using known means, or, for example, using reactions as or similar to those described below.
  • a range of dimethylethanolamine salts and ionic liquids can be synthesised from dimethylethanolamine and alkyl halides, followed by exchange of the halide ion for other anions.
  • These ionic liquids are useful because dimethylethanolamine is cheap, stable, and the oxygen functionality lowers the melting point of these ammonium salts compared with similar tetra-alkylammonium salts.
  • This material is a room temperature ionic liquid.
  • the product in the first step of Scheme 2 can be alkylated with a different alkyl halide. This is shown in Scheme 3, below.
  • Ethyl DABCO methanesulfonate [C 2 DABCO][OSO 2 CH 3 ] (mp 81° C.) and hexyl DABCO methanesulfonate have also been synthesised from the reaction of DABCO and ethylmethanesulfonate or hexylmethanesulfonate.
  • Diazobicyclo-[2,2,0]-octene (1.13 g, 12.5 mmol) and alkyl bromide (10 mmol) were heated under reflux (or at 150° C. which ever is the lower) for 1 to 24 hours. On cooling a precititate formed. This was dissolved in a minimum quantity of boiling ethyl acetate/isopropanol for C 2 to C 10 DABCO bromides and boiling toluene/ethyl acetate for C 12 to C 18 DABCO bromides. The crystals that formed on cooling were filtered off and dried by heating at 80° C. for 4 hours under vacuum (1 mmHg). The compounds were analysed by NMR and DSC. Yields typically 60-80%
  • Diazobicyclo-[2,2,0]-octene (1.13 g, 12.5 mmol) and alkyl methanesulfonate (10 mmol) were heated at 100° C. for 1 hour. On cooling a precititate formed. This was dissolved in a minimum quantity boiling ethyl acetate/isopropanol. The crystals that formed on cooling were filtered off and dried by heating at 80° C. for 4 hours under vacuum (1 mmHg). The compounds were analysed by NMR and DSC. Yields typically 70-80%
  • Tetramethylethylenediamine (TMEDA) ionic liquids can be synthesised from TMEDA and an alkyl bromide as below.
  • the C 2 , C 5 , C 6 , C 8 , C 12 and C 18 alkyl bromides have been made and appear slightly lower melting than the DABCO ionic liquids.
  • TEDA Tetramethylethylenediamine
  • alkyl bromide 25 mmol
  • [C 2 TMEDA]Br and [C 4 TMEDA]Br a crystalline solid formed and for [C 18 TMEDA]Br, a liquid crystalline material formed.
  • DMAP N,N-dimethylaminopyidine
  • DMAP Dimethylaminopyridine
  • ethyl or hexyl methanesulfonate 25 mmol
  • ethyl or hexyl methanesulfonate 25 mmol
  • ethyl or hexyl methanesulfonate 25 mmol
  • a precititate formed. This was dissolved in a minimum quantity boiling ethyl acetate/isopropanol for C 2 to C 6 DMAP methanesulfonates.
  • the crystals that formed on cooling were filtered off and dried by heat at 80° C. for 4 hours under vacuum (1 mmHg).
  • the compounds were analysed by NMR and DSC. Yields typically 80-85%.
  • the 1-chloro-2-(diisopropylamino)ethane hydrochloride was used to alkylate dimethylaminoethanol, the resulting diamine was alkylated with propyl bromide.
  • the quaternisation reaction itself is regiospecific, the diisopropylamino group is non-nucleophilic and cannot be quaternised under the applied conditions.
  • the obtained salt shows a five atom chain between the cation and the basic diisopropylamino group.
  • the metathesis reaction with lithium bistriflimide gave a room temperature ionic liquid. Its structure is shown below.
  • the above scheme shows a synthesis of a range of basic ionic liquids, for example, bearing a 5-atom spacer between the quaternary nitrogen and the basic nitrogen.
  • the general synthetic strategy for the preparation of BIL 1-4 is simple and versatile and is shown in the Scheme above.
  • a vital part of the synthesis of the base-tethered ionic liquids involves the use of 2-diisopropylaminoethyl chloride reacting with a chosen nucleophilic reagent and is facilitated by the neighbouring group participation from the diisopropylamino moiety.
  • the synthetic strategy for the preparation of BIL 1, 2 and 4 takes into account the ability to selectively quaternise the pendant amino, imidazolyl or pyridyl groups as against the diisopropylalkylamino group which is non-nucleophilic in nature.
  • the synthetic strategy for the preparation of BIL 3 makes use of the insolubility of the mono-quaternised diamine which precipitates out of toluene (solvent) thereby preventing it from further reaction with the alkyl halide.
  • the halide anion associated with the quaternary ammonium salts was subjected to metathesis with lithium bis-triflimide to generate base tethered ionic liquids BIL 1-4.
  • the esterification reaction (Reaction 1) is an equilibrium reaction driven to completion by using an excess of methanol. As can be seen, water is the only byproduct.
  • the advantage of this method is that the ionic liquid/water methanol mixture obtained at the end of the reaction is immiscible with the FAME product and forms a separate phase (Reaction 1b).
  • the bio-diesel is isolated by phase separation.
  • Another advantage of this reaction is that the reaction occurs at room temperature and hence no energy input is required in this step.
  • the catalysts (1) and (4) ⁇ 4-(3-methylimidazolium)butanesulfonic acid bistrifluoromethanesulfonylamide and 4-(3-methylimidazolium)butanesulfonic acid trifluoromethanesulfonate ⁇ catalyse the reaction well at 120° C. (Table 3).
  • This reaction was performed in the microwave over and under pressure to stop the methanol form evaporating.
  • p-TSA conventional acid para-toluenesulfonic acid
  • the ionic liquids have the advantage that they are not volatile and remain in the methanol/glycerol layer.
  • the acid catalysts (2) and (3) are less effective and require higher reaction temperatures to catalyse the reaction. Hence this reaction provides a method for measuring the acidity of these new acidic ionic liquids.
  • Table 4 shows that the reaction is temperature dependent and at least 120° C. is needed to give over the required 95% conversion to meet the bio-diesel specification.
  • the product forms a separate layer on the surface of the methanol/glycerol layer/ionic liquid layer as shown in FIG. 2 .
  • Animal fat (lard—a triglyceride of mostly oleic acid) (1.0 g), methanol (2.0 g) and catalyst (0.25 g) (unless otherwise stated) (selected from (1) to (7) above) was placed in a microwave tube with a magnetic stirrer flea and heated to the desired temperature for the desired time (See Tables 3, 4 and 5) for conditions. This was cooled to room temperature and the two layers were analysed by NMR (CDCl 3 for fat layer and CD 3 OD for methanol layer). The yield was determined by comparing the integration of the —CH 2 — group in the glyceride with the OCH 3 group in the methyl ester of methyl oleate (bio-diesel) (see FIGS. 3 to 5 ).
  • Catalyst recycling Methanol and water or glycerol were separated from the catalyst by distillation or vacuum distillation. The catalyst could be then recycled and reused.
  • Rape seed oil (1.0 g), methanol (2.5, 5.0 or 10.0 fold excess) and catalyst ([emim][HSO 4 ]) (1.0 mol %, 2.5 mol % or 5.0 mol %) was placed in a glass tube with a magnetic stirrer flea. This was stirrer at room temperature (20° C.) and the samples were analyses by GC after 2 hours, 4 hours and 144 hours (this was assumed to be long enough for equilibrium to be established) (See Tables 1 and 2; Reaction 1b; and FIG. 1 for conditions). The two layers were also analysed by NMR (CDCl 3 for fat layer and (CD 3 OD for methanol layer). The yield was determined by comparing the integration of the —CH 2 — group in the glyceride with the OCH 3 group in the methyl ester of methyl oleate (bio-diesel).
  • transesterification For the acid catalysed transesterification of animal fat with methanol, higher reaction temperatures are needed (typically 90 to 160° C.).
  • the transesterification can be carried out with an acidic or basic ionic liquid, with the acidic ionic liquids giving better results.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fats And Perfumes (AREA)
  • Catalysts (AREA)
US11/908,313 2005-03-11 2006-02-27 Production of Bio-Diesel Abandoned US20090235574A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0505064.6A GB0505064D0 (en) 2005-03-11 2005-03-11 Production of bio-diesel
GB0505064.6 2005-03-11
PCT/GB2006/000682 WO2006095134A1 (en) 2005-03-11 2006-02-27 Production of bio-diesel

Publications (1)

Publication Number Publication Date
US20090235574A1 true US20090235574A1 (en) 2009-09-24

Family

ID=34508931

Family Applications (1)

Application Number Title Priority Date Filing Date
US11/908,313 Abandoned US20090235574A1 (en) 2005-03-11 2006-02-27 Production of Bio-Diesel

Country Status (5)

Country Link
US (1) US20090235574A1 (https=)
EP (1) EP1866086A1 (https=)
JP (1) JP2008533232A (https=)
GB (1) GB0505064D0 (https=)
WO (1) WO2006095134A1 (https=)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100048829A1 (en) * 2006-10-13 2010-02-25 Basf Aktiengesellschaft Ionic liquids for solubilizing polymers
KR101125638B1 (ko) * 2010-01-13 2012-03-27 에이치플러스에코 주식회사 중유 에멀젼용 분산 유화제 및 이를 포함하는 중유 에멀젼 연료유
CN102872911A (zh) * 2012-10-23 2013-01-16 吴峰 一种离子液体催化剂及脂肪酸制备方法
CN103074389A (zh) * 2013-02-04 2013-05-01 东莞市合能微生物能源有限公司 一种利用生物酶制备生物柴油的方法
US8580886B2 (en) 2011-09-20 2013-11-12 Dow Corning Corporation Method for the preparation and use of bis (alkoxysilylorgano)-dicarboxylates
US20150191665A1 (en) * 2012-06-07 2015-07-09 Hitachi, Ltd. Fuel synthesizing method and fuel synthesizing apparatus
US20150316519A1 (en) * 2014-05-05 2015-11-05 Uop Llc Method for quantitation of acid sites in acidic ionic liquids using silane and borane compounds
US20150316518A1 (en) * 2014-05-05 2015-11-05 Uop Llc Method for quantitation of acid sites in acidic catalysts using silane and borane compounds
US9518072B2 (en) 2011-12-02 2016-12-13 Dow Corning Corporation Ester-functional silanes and the preparation and use thereof; and use of iminium compounds as phase transfer catalysts
WO2017009578A1 (fr) * 2015-07-16 2017-01-19 Université de Bourgogne Procédé de préparation de liquides ioniques biosources pour la catalyse
US10233141B2 (en) * 2014-06-13 2019-03-19 Southern Biofuel Technology Pty Ltd Process for the preparation of fatty acid alkyl esters
US12612404B2 (en) 2022-12-15 2026-04-28 Industrial Technology Research Institute Ionic compound, absorbent and absorption device

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100746996B1 (ko) 2006-09-06 2007-08-08 인하대학교 산학협력단 이온성 액체를 이용한 바이오디젤 및 글리세롤의 생산 방법
US8598378B2 (en) 2008-03-14 2013-12-03 University Of Hawaii Methods and compositions for extraction and transesterification of biomass components
KR101115283B1 (ko) 2009-10-15 2012-03-13 대상 주식회사 오메가-3 불포화 지방산과 아스코르빈산과의 복합체의 제조방법
EP2433970A1 (en) 2010-09-28 2012-03-28 Cargill, Incorporated Microprocessing for preparing a polycondensate
CN106433994B (zh) * 2016-08-23 2021-04-02 河北工程大学 一种聚合离子液体催化制备生物柴油的方法
JP2024522789A (ja) * 2021-06-18 2024-06-21 フラオンホファー－ゲゼルシャフト・ツア・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファオ 硫酸化多糖を調製するための方法、および硫酸化多糖

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030163952A1 (en) * 2003-02-19 2003-09-04 Alan Rae Compositions
US20040035293A1 (en) * 2002-04-05 2004-02-26 Davis James Hillard Functionalized ionic liquids, and methods of use thereof
US20040231234A1 (en) * 2003-05-19 2004-11-25 May Choo Yuen Palm diesel with low pour point for climate countries

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3682751B2 (ja) * 1997-12-24 2005-08-10 ジヤトコ株式会社 エステル燃料製造方法及びその装置
JP4052748B2 (ja) * 1999-01-13 2008-02-27 旭化成株式会社 エステル組成物及び製造方法
JP2001247572A (ja) * 2000-03-06 2001-09-11 Central Glass Co Ltd ピリミジン誘導体塩
JP2001247508A (ja) * 2000-03-06 2001-09-11 Central Glass Co Ltd オレフィン化合物の製造方法
JP2002275118A (ja) * 2001-03-15 2002-09-25 Central Glass Co Ltd アルドール反応生成物の製造方法
DE10145747A1 (de) * 2001-09-17 2003-04-03 Solvent Innovation Gmbh Ionische Flüssigkeiten
JP4184974B2 (ja) * 2002-02-20 2008-11-19 株式会社レボインターナショナル ディーゼル燃料用脂肪酸アルキルエステルの製造方法
DE10208822A1 (de) * 2002-03-01 2003-09-11 Solvent Innovation Gmbh Halogenfreie ionische Flüssigkeiten
CN100497526C (zh) * 2005-07-08 2009-06-10 中国科学院过程工程研究所 基于离子液体的生物柴油合成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040035293A1 (en) * 2002-04-05 2004-02-26 Davis James Hillard Functionalized ionic liquids, and methods of use thereof
US20030163952A1 (en) * 2003-02-19 2003-09-04 Alan Rae Compositions
US20040231234A1 (en) * 2003-05-19 2004-11-25 May Choo Yuen Palm diesel with low pour point for climate countries

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100048829A1 (en) * 2006-10-13 2010-02-25 Basf Aktiengesellschaft Ionic liquids for solubilizing polymers
US8044120B2 (en) * 2006-10-13 2011-10-25 Basf Aktiengesellschaft Ionic liquids for solubilizing polymers
KR101125638B1 (ko) * 2010-01-13 2012-03-27 에이치플러스에코 주식회사 중유 에멀젼용 분산 유화제 및 이를 포함하는 중유 에멀젼 연료유
US8580886B2 (en) 2011-09-20 2013-11-12 Dow Corning Corporation Method for the preparation and use of bis (alkoxysilylorgano)-dicarboxylates
US9518072B2 (en) 2011-12-02 2016-12-13 Dow Corning Corporation Ester-functional silanes and the preparation and use thereof; and use of iminium compounds as phase transfer catalysts
US20150191665A1 (en) * 2012-06-07 2015-07-09 Hitachi, Ltd. Fuel synthesizing method and fuel synthesizing apparatus
CN102872911A (zh) * 2012-10-23 2013-01-16 吴峰 一种离子液体催化剂及脂肪酸制备方法
CN103074389A (zh) * 2013-02-04 2013-05-01 东莞市合能微生物能源有限公司 一种利用生物酶制备生物柴油的方法
US20150316518A1 (en) * 2014-05-05 2015-11-05 Uop Llc Method for quantitation of acid sites in acidic catalysts using silane and borane compounds
US9435779B2 (en) * 2014-05-05 2016-09-06 Uop Llc Method for quantitation of acid sites in acidic ionic liquids using silane and borane compounds
US9435688B2 (en) * 2014-05-05 2016-09-06 Uop Llc Method for quantitation of acid sites in acidic catalysts using silane and borane compounds
US20150316519A1 (en) * 2014-05-05 2015-11-05 Uop Llc Method for quantitation of acid sites in acidic ionic liquids using silane and borane compounds
US10233141B2 (en) * 2014-06-13 2019-03-19 Southern Biofuel Technology Pty Ltd Process for the preparation of fatty acid alkyl esters
WO2017009578A1 (fr) * 2015-07-16 2017-01-19 Université de Bourgogne Procédé de préparation de liquides ioniques biosources pour la catalyse
FR3038853A1 (fr) * 2015-07-16 2017-01-20 Univ Bourgogne Utilisation de liquides ioniques recyclables comme catalyseurs d'esterification
US12612404B2 (en) 2022-12-15 2026-04-28 Industrial Technology Research Institute Ionic compound, absorbent and absorption device

Also Published As

Publication number Publication date
GB0505064D0 (en) 2005-04-20
EP1866086A1 (en) 2007-12-19
WO2006095134A1 (en) 2006-09-14
JP2008533232A (ja) 2008-08-21

Similar Documents

Publication Publication Date Title
US20090235574A1 (en) Production of Bio-Diesel
De Santi et al. Novel Brønsted acidic deep eutectic solvent as reaction media for esterification of carboxylic acid with alcohols
Chinnappan et al. Environmentally benign catalyst: Synthesis, characterization, and properties of pyridinium dicationic molten salts (ionic liquids) and use of application in esterification
Himmler et al. Transesterification of methylsulfate and ethylsulfate ionic liquids—an environmentally benign way to synthesize long-chain and functionalized alkylsulfate ionic liquids
CN101137436B (zh) 碱稳定性离子液体
Wang et al. Epoxidation of soybean oil catalyzed by deep eutectic solvents based on the choline chloride–carboxylic acid bifunctional catalytic system
Nowicki et al. Novel basic ionic liquids from cyclic guanidines and amidines–new catalysts for transesterification of oleochemicals
EP1425268A1 (de) Organische sulfate als ionische flüssigkeiten
KR20090105375A (ko) 다양한 극성/비극성 용매 혼화성 이온성 액체 및 그의제조방법
Chen et al. Self-solidifying quaternary phosphonium-containing ionic liquids as efficient and reusable catalysts for biodiesel production
CA2466780C (en) Preparation of ionic liquids
CA2750448A1 (en) Novel tricyanoborates
JP2008533232A5 (https=)
Mukesh et al. Production of C-14 levulinate ester from glucose fermentation liquors catalyzed by acidic ionic liquids in a solvent-free self-biphasic system
EP2223915A1 (en) Ionic liquid solvents
GB2502607A (en) Process for the preparation of ionic liquids
CN101456844A (zh) 含磺酸酯基侧链室温离子液体及其制备方法和应用
CN101024612B (zh) 一种酸性离子液体催化醇酸酯化方法
CN101514292A (zh) 一种离子液体催化制备微生物柴油的方法
EP1373280A1 (en) Phosphonium phosphinate compounds and their preparation
CN103819447B (zh) 一种由甘油制备甘油缩酮酯的方法
US9920003B2 (en) Non-ionic amphiphiles and methods of making the same
CN104624242B (zh) 一种合成生物柴油酸性离子液体固载型催化剂及其制备方法
Elsheikh et al. Evaluation of catalytic activity of two functionalized imidazolium ionic liquids for biodiesel fuel production by a two‐stage process
CN100567259C (zh) 一种制备亚硫酸亚乙酯的方法

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION