EP1866086A1 - Production of bio-diesel - Google Patents

Production of bio-diesel

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Publication number
EP1866086A1
EP1866086A1 EP06709909A EP06709909A EP1866086A1 EP 1866086 A1 EP1866086 A1 EP 1866086A1 EP 06709909 A EP06709909 A EP 06709909A EP 06709909 A EP06709909 A EP 06709909A EP 1866086 A1 EP1866086 A1 EP 1866086A1
Authority
EP
European Patent Office
Prior art keywords
bas
cation
cat
neutral
aryl
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.)
Withdrawn
Application number
EP06709909A
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German (de)
English (en)
French (fr)
Inventor
Martin John Earle
Kenneth Richard Seddon
Natalia Vladimirovna 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.)
Queens University of Belfast
Original Assignee
Queens University of Belfast
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Filing date
Publication date
Application filed by Queens University of Belfast filed Critical Queens University of Belfast
Publication of EP1866086A1 publication Critical patent/EP1866086A1/en
Withdrawn legal-status Critical Current

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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 (Ze: 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. Many syntheses of bio-diesel are known, typically using acid or base catalysis.
  • 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 Br ⁇ nsted 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 0 C. Such compositions are mixtures of components which are often liquid at temperatures below the individual melting points of the components.
  • base refers to Br ⁇ nsted 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 Br ⁇ nsted 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:
  • Cat* is a cation ic species comprising or consisting of ammonium, phosphonium, pyrazolium, DBU or DBN;
  • Z is a covalent bond joining Cat * and Bas or 1 , 2 or 3 aliphatic linking groups each containing 1 to 10 carbon atoms and each optionally one, two or three oxygen atoms;
  • Bas is a basic moiety.
  • 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(RO(R 2 ), and -P(Ri)(R 2 ); and wherein Ri 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, /so-propyl, butyl, seo-butyl, /so-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 Ci to Ci 8 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 -CH2-CH 2 -CH 2 -CH 2 )-,-(CH 2 -CH2-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:
  • Bas and Z are as defined above;
  • R b , R c , and R d can be the same or different, and are each independently selected from hydrogen, a C 1 to C 40 , straight chain or branched alkyl group, a C 3 to C 8 cycloalkyl group, or a C 6 to Cio aryl group, wherein said alkyl, cycloalkyl or aryl groups are either unsubstituted or may be substituted by one to three groups selected from: C 1 to Ce alkoxy, Ce to C 10 aryl, CN, OH, NO 2 , C 7 to C 30 aralkyl and C 7 to C 30 alkaryl.
  • Cat + -Z-Bas is selected from:
  • Caf-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:
  • Caf-Z-Bas may be selected from:
  • Cat + -Z-Bas may also be:
  • Bas, Z and R b are as defined above.
  • 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
  • [X 1 J is [OH] " .
  • the acidic cation preferably has the formula:
  • Cat + is a cationic species
  • Z is a covalent bond joining Cat + and Acid containing 1 to 10 carbon atoms and each optionally one, two or three oxygen atoms;
  • Acid is an acidic moiety. Acid is preferably selected from -SO 3 H, -CO 2 H, -SO 3 -Ph-R 1 -SO 3 R, RP0(0H)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, pyridini ⁇ m, 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
  • [Caf] 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
  • [Caf] may comprise or consist of a heterocyclic ring structure selected from pyrazolium, isothiazolinium, tetrazolium, piperidinium, morpholinium and pyrrolidinium.
  • Cat + -Z-Acid is selected from:
  • Acid and Z are as defined above;
  • R b , R c , R d , R e , R f , R g and R h can be the same or different, and are each independently selected from hydrogen, a Ci to C 4 O 1 straight chain or branched alkyl group, a C 3 to C 8 cycloalkyl group, or a C 6 to Ci 0 aryl group, wherein said alkyl, cycloalkyl or aryl groups are unsubstituted or may be substituted by one to three groups selected from: Ci to C 6 alkoxy, C 6 to C 10 aryl, CN, OH, NO 2 , C 7 to C 30 aralkyl and C 7 to C 30 alkaryl, or any two of R b , R c , R d , R e and R f attached to adjacent carbon atoms form a methylene chain -(CH2) q - wherein q is from 8 to 20.
  • Cat + -Z-Acid is selected from:-
  • Acid and Z are as defined above;
  • R b , R c , R d , R e , R f , R 3 and R h can be the same or different, and are each independently selected from hydrogen, a Ci to C 4O , straight chain or branched alkyl group, a C 3 to Cs cycloalkyl group, or a C 6 to Ci 0 aryl group, wherein said alkyl, cycloalkyl or aryl groups are unsubstituted or may be substituted by one to three groups selected from: Ci to C 6 alkoxy, C 6 to C 10 aryl, CN, OH, NO 2 , C 7 to C 30 aralkyl and C 7 to C 3O alkaryl, or any two of R b , R c , R d , R e and R f attached to adjacent carbon atoms form a methylene chain -(CH2) q - wherein q is from 8 to 20.
  • Cat + -Z-Acid is:
  • [X 3 ]- 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:
  • R a , R b , R c , and R d can be the same or different, and are each independently selected from hydrogen, a C 1 to C 40 , straight chain or branched alkyl group, a C 3 to C 8 cycloalkyl group, or a C 6 to Cio aryl group, wherein said alkyl, cycloalkyl or aryl groups are unsubstituted or may be substituted by one to three groups selected from: Ci to C 6 alkoxy, C 6 to Cio aryl, CN, OH, NO 2 , C 7 to C 3 o aralkyl and C 7 to C 30 alkaryl. More preferably, the neutral cation is selected from:
  • R a is as defined above.
  • 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:
  • R a , R b , R c , R d are a Ci to C 40 , straight or branched, alkyl group
  • 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, benzof uranium, dibenzofurariium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperaz
  • 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, oxaphosphoiium, pyrollium, borolium, furanium, thiophenium, phospholium, pentazolium, indolium, indolinium, oxazolium, isooxazolium, isotriazolium, tetrazol ⁇ um, benzofuranium, dibenzofuranium, benzothiophenium, dibenzothiophenium, thiadiazolium, pyrimidinium, pyrazinium, pyridazinium, piperazinium, piperidin
  • 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:-
  • R a , R b , R G , R d , R e , R f , R g and R h can be the same or different, and are each independently selected from hydrogen, a Ci to C 40 , straight chain or branched alkyl group, a C 3 to Ce cycloalkyl group, or a Ce to C 10 aryl group, wherein said alkyl, cycloalkyl or aryl groups are unsubstituted or may be substituted by one to three groups selected from: Ci to C 6 alkoxy, C 6 to C 10 aryl, CN, OH, NO 2 , C 7 to C30 aralkyl and C 7 to C 30 alkaryl, or any two of Fc b, D Rc , R d , R e and R f attached to adjacent carbon atoms form a methylene chain -(CH 2 ) q - wherein q is from 8 to 20.
  • the neutral cation is selected from:
  • R a , R b , R c , R d , R e , R f , R 9 and R h are as defined above.
  • 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 Ci to C 6 alkyl, or Ci 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 biodiesel to be easily separated from the ionic liquid, and the ionic liquid phase can then be recycled.
  • solvents such as methanol, water or ethanol
  • Figure 2 is a picture showing a separate methyl oleate (upper layer) product layer, wherein the left tube is before reaction (methanol/glycerol/[MIBS][OTfj, and the right after reaction;
  • Figure 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;
  • Figure 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;
  • Figure 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 tefra-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 (1.13g, 12.5 mmol) and alkyl bromide (10 mmol) were heated under reflux (or at 150 0 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 Cio DABCO bromides and boiling toluene/ethyl acetate for C 12 to Ci 8 DABCO bromides. The crystals that formed on cooling were filtered off and dried by heating at 80 0 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 10O 0 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 0 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 beiow.
  • the C 2 , C 5 , C 6 , C 8 , C 12 and Ci 8 alkyl bromides have been made and appear slightly lower melting than the DABCO ionic liquids.
  • TMEDA Tetramethylethylenediamine
  • alkyl bromide 25 mmol
  • [C 2 TMEDA]Br and [C 4 TMEDA]Br a crystalline solid formed and for [Ci ⁇ TMEDA]Br, a liquid crystalline material formed.
  • DMAP 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 8O 0 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- quatemised 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.
  • Reaction 1b The phase behaviour change during Reaction 1a.
  • the catalysts (1) and (4) ⁇ 4-(3-methylimidazolium)butanesulfonic acid bistrifluoromethanesulfonylamide and 4-(3-methylimidazolium)butanesulfonic acid trifluoromethanesulfonate ⁇ catalyse the reaction well at 120 0 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.
  • Animal fat (lard - a triglyceride of mostly oleic acid) (1.Og), methanol (2.Og) and catalyst (0.25g) (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 (CDCb for fat layer and CD 3 OD for methanol layer). The yield was determined by comparing the integration of the -CH2- group in the glyceride with the OCH 3 group in the methyl ester of methyl oleate (bio-diesel) (see Figures 3 to 5).
  • Rape seed oil (1.O g), methanol (2.5, 5.0 or 1O.0 fold excess) and catalyst ([emim][HS0 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 0 C) and the samples were analyses by GC after 2hours, 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 Figure 1 for conditions). The two layers were also analysed by NMR (CDCI 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 0 C).
  • the transesterification can be carried out with an acidic or basic ionic liquid, with the acidic ionic liquids giving better results.

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