WO2015079117A1 - Method for enzyme recovery in biofuel production process - Google Patents
Method for enzyme recovery in biofuel production process Download PDFInfo
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- WO2015079117A1 WO2015079117A1 PCT/FI2014/050926 FI2014050926W WO2015079117A1 WO 2015079117 A1 WO2015079117 A1 WO 2015079117A1 FI 2014050926 W FI2014050926 W FI 2014050926W WO 2015079117 A1 WO2015079117 A1 WO 2015079117A1
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- phase
- intermediate product
- product mixture
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- cationic polymer
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- 108090000790 Enzymes Proteins 0.000 title claims abstract description 42
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002551 biofuel Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 title claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000013067 intermediate product Substances 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 23
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 20
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 14
- -1 fatty acid esters Chemical class 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 229920002401 polyacrylamide Polymers 0.000 claims description 12
- 239000003225 biodiesel Substances 0.000 claims description 9
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 5
- 239000008158 vegetable oil Substances 0.000 claims description 5
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 102000004882 Lipase Human genes 0.000 claims description 3
- 108090001060 Lipase Proteins 0.000 claims description 3
- 239000004367 Lipase Substances 0.000 claims description 3
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical group [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 3
- 239000003925 fat Substances 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 235000019421 lipase Nutrition 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 description 7
- 239000000178 monomer Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 108010093096 Immobilized Enzymes Proteins 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- 238000006105 Hofmann reaction Methods 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- NRWCNEBHECBWRJ-UHFFFAOYSA-M trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)C NRWCNEBHECBWRJ-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/145—Extraction; Separation; Purification by extraction or solubilisation
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/14—Hydrolases (3)
- C12N9/16—Hydrolases (3) acting on ester bonds (3.1)
- C12N9/18—Carboxylic ester hydrolases (3.1.1)
- C12N9/20—Triglyceride splitting, e.g. by means of lipase
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- the invention relates to a method for enzyme recovery in biofuel production process employing enzyme catalysts according to the preamble of enclosed independent claim.
- Biodiesel is produced from various feedstocks, either from virgin oil feedstocks, such as soybean oil, or from waste feedstocks, such as waste vegetable oils, grease, animal fats.
- biodiesel is normally produced from the different feedstocks by using acidic and/or alkali catalysts.
- Triglycerides as well as di- and monoglycerides react with an alcohol in the presence of a catalyst to produce an intermediate product mixture comprising fatty acid esters and glycerol. This reaction is called transesterification.
- enzyme catalysts in the production of biofuel, such as biodiesel.
- use of enzymes in biofuel, e.g. biodiesel production provides a number of advantages, such as smaller energy consumption and high quality glycerol by-product.
- the drawback of the processes, which employ enzyme catalysts is the price of the enzymes. Therefore it would be economically advantageous to be able to recycle the enzymes in the biofuel production process.
- immobilized enzymes are used in biofuel production. Immobilized enzymes are bound to a solid surface of a carrier, such as ceramic beads or ion- exchange resins. Immobilization of enzymes may reduce the mass-transfer rate of the biofuel reaction and even further increase the enzyme costs.
- Liquid enzymes which are immersed in the liquid reaction medium and not bound to any carrier particle, would be an interesting alternative for biofuel production. Their mass transfer resistance is negligible and no addition of solid carrier system, which may impede the transesterification reaction, is needed. However, the difficulty of separating and recovering the liquid enzymes from the intermediate product mixture has seriously limited the interest to use liquid enzymes, at least for commercial scale production.
- An object of the present invention is to minimise or even completely eliminate the problems existing in the prior art.
- One object of the present invention is thus to provide a method, with which the enzyme can be easily separated from the intermediate product mixture and optionally recycled back in the process.
- Typical method according to the present invention for enzyme recovery in biofuel production process comprises
- the emulsion phase comprising liquid enzymes
- liquid enzymes are effectively concentrated to an emulsion phase, which is formed when an anionic or non-ionic surfactant and a cationic polyacrylamide are added to an intermediate product mixture in biofuel production process.
- the emulsion phase with liquid enzymes may be formed between the lighter top phase comprising fatty acid esters (FAE) and heavier bottom phase comprising glycerol.
- FAE fatty acid esters
- the top phase is separated and transferred to biofuel processing and the bottom phase is separate and transferred to a further processing step.
- the emulsion phase which comprises liquid enzymes, is easily separated from the top and bottom phase and the enzymes can be recycled back to process if desired.
- intermediate product mixture is understood as a liquid mixture which comprise at least transesterification products, i.e. fatty acid esters (FAE); glycerol; liquid enzymes.
- the intermediate product mixture may further comprise water and/or residual alcohol.
- the invention is suitable for biofuel production by transesterification with liquid enzymes, such as lipases.
- liquid enzymes such as lipases.
- liquid enzymes is understood as enzymes that are free from attachment to surfaces of carrier elements, such as particles, and which are fully immersed into the reaction mixture. Liquid enzymes are fully dispersed in the reaction mixture, whereby they have good contact between the phases.
- the separation of the emulsion phase comprising liquid enzymes from the bottom phase is performed by gravity sedimentation.
- centrifugation may be used, but it is not necessary.
- the sedimentation time may vary between a few minutes up to a few hours, depending on the batch size.
- the anionic or non-ionic surfactant and the cationic polymer may be added to the intermediate product mixture in any order. In other words, it is possible to first add the anionic or non-ionic surfactant and then the cationic polymer, or alternatively to add first the cationic polymer and then the anionic or non-ionic surfactant.
- the anionic surfactant or non-ionic surfactant and the cationic polymer are added simultaneously to the intermediate product mixture.
- the anionic or non-ionic surfactant may be added in any suitable amount.
- the anionic surfactant may be added in amount up to 2800 ppm, normally in amount of 0.7 - 1400 ppm, preferably 140 - 420 ppm, more preferably 280 - 350 ppm, given as active agent.
- Anionic or non-ionic surfactant is usually used in form of a solution.
- an anionic surfactant and a cationic polymer are added to the intermediate product mixture.
- the anionic surfactant may be selected from linear alkyl sulphates, branched alkyl sulphates, sulphosuccinates, linear alkyl benzene sulphonates, branched alkyl benzene sulphonates, alkylnaphthalenesulphonat.es and alkyldiphenyloxide disulphonates.
- the anionic surfactant is sodium dioctyl sulphosuccinate.
- the non-ionic surfactant may be selected from suitable ethoxylates.
- the cationic polymer may be selected from a group comprising cationic polyacrylamide, polydiallyldimethylammonium chloride (poly-DADMAC), polyamine, cationic starch and chitosan.
- the cationic polymer is cationic polyacrylamide.
- Cationic polyacrylamide may be obtained by copolymerizing acrylamide with a cationic monomer or methacrylamide with a cationic monomer.
- the cationic monomer may be selected from the group consisting methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, 3-(methacrylamido) propyltrimethyl ammonium chloride, 3- (acryloylamido) propyltrimethyl ammonium chloride, diallyldimethyl ammonium chloride, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, and similar monomers.
- cationic polyacrylamide is copolymer of acrylamide or methacrylamide with (meth)acryloyloxyethyltrimethyl ammonium chloride.
- Cationic polyacrylamide may also contain other monomers, as long as its net charge is cationic and it has an acrylamide/methacrylamide backbone.
- An acrylamide or methacrylamide based polymer may also be treated after the polymerisation to render it cationic, for example, by using Hofmann or Mannich reactions
- Cationic polyacrylamide may have charge density of 0.15 - 4.0 meq/g, preferably 0.5 - 3.5 meq/g, more preferably 1 .5 - 3.0 meq/g.
- the cationic polymer such as cationic polyacrylamide, may be added in any suitable amount, for example in amount up to 4000 ppm, normally in amount of 1 - 2000 ppm, preferably 200 - 600 ppm, more preferably 200 - 400 ppm, given as active agent.
- the cationic polymer is used in form of dry powder.
- the present invention is especially suitable for processes where biodiesel is produced by reacting glycerides (tri-, di-, mono-) with methanol in the presence of a liquid enzyme catalyst to produce an intermediate product mixture comprising fatty acid methyl esters (FAME) and glycerol.
- glycerides tri-, di-, mono-
- FAME fatty acid methyl esters
- the present invention is also suitable for biofuel production process, which comprises transesterification with liquid enzymes, such as lipases, from virgin vegetable oil feedstocks, such as soybean oil, or from waste feedstocks, such as waste vegetable oils, grease, animal fats.
- liquid enzymes such as lipases
- a batch of biodiesel was prepared in lab scale.
- the batch was a two-phase mixture composed of the clear top phase of fatty acid methyl ester (FAME), and of the emulsion phase at the bottom of the reaction vessel. After the separation of the top phase, about 1 litre of intermediate product mixture was left for lab trials.
- FAME fatty acid methyl ester
- Anionic surfactant comprising sodium dioctyl sulphosuccinate (KemFoamX 2970, Kemira Oyj) and cationic polyacrylamide flocculant (Superfloc C494, Kemira Oyj) were used in the experiments.
- Anionic surfactant was diluted to 10 weight-% aqueous solution and cationic polymer was diluted to 0.5 weight-% aqueous solution
- anionic surfactant and cationic polymer were added successively to 500 ml of intermediate product mixture upon fast mixing at room temperature. Fast mixing was continued for 5 minutes. After the mixing period, the mixture was allowed to settle for 30 minutes.
- emulsion phase was situated between a top phase comprising fatty acid methyl ester (FAME) and a bottom phase comprising glycerol.
- the bottom phase comprising glycerol could be easily separated from emulsion phase by using gravity settling.
- the top phase comprising FAME can be separated for further processing for biodiesel.
- the emulsion phase comprising liquid enzymes can be recycled back to the process.
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Abstract
The invention relates to a method for enzyme recovery in biofuel production process. The method comprises steps of producing, by using liquid enzymes, an intermediate product mixture comprising a top phase comprising fatty acid esters and a bottom phase comprising glycerol; adding cationic polymer and an anionic surfactant or non-ionic surfactant to the intermediate product mixture; allowing an emulsion phase to form, the emulsion phase comprising liquid enzymes; and separating the emulsion phase from the intermediate product mixture.
Description
METHOD FOR ENZYME RECOVERY IN BIOFUEL PRODUCTION PROCESS
The invention relates to a method for enzyme recovery in biofuel production process employing enzyme catalysts according to the preamble of enclosed independent claim.
There is an increasing interest in biofuel production, especially biodiesel production, as biofuels are becoming an alternative for traditional petroleum products.
Biodiesel is produced from various feedstocks, either from virgin oil feedstocks, such as soybean oil, or from waste feedstocks, such as waste vegetable oils, grease, animal fats. In commercial scale biodiesel is normally produced from the different feedstocks by using acidic and/or alkali catalysts. Triglycerides as well as di- and monoglycerides react with an alcohol in the presence of a catalyst to produce an intermediate product mixture comprising fatty acid esters and glycerol. This reaction is called transesterification.
It is possible to use enzyme catalysts in the production of biofuel, such as biodiesel. In fact, use of enzymes in biofuel, e.g. biodiesel, production provides a number of advantages, such as smaller energy consumption and high quality glycerol by-product. The drawback of the processes, which employ enzyme catalysts, is the price of the enzymes. Therefore it would be economically advantageous to be able to recycle the enzymes in the biofuel production process. At the present immobilized enzymes are used in biofuel production. Immobilized enzymes are bound to a solid surface of a carrier, such as ceramic beads or ion- exchange resins. Immobilization of enzymes may reduce the mass-transfer rate of the biofuel reaction and even further increase the enzyme costs. Liquid enzymes, which are immersed in the liquid reaction medium and not bound to any carrier particle, would be an interesting alternative for biofuel production. Their mass transfer resistance is negligible and no addition of solid carrier system, which may impede the transesterification reaction, is needed. However, the
difficulty of separating and recovering the liquid enzymes from the intermediate product mixture has seriously limited the interest to use liquid enzymes, at least for commercial scale production. An object of the present invention is to minimise or even completely eliminate the problems existing in the prior art.
One object of the present invention is thus to provide a method, with which the enzyme can be easily separated from the intermediate product mixture and optionally recycled back in the process.
These objects are attained with a method and an arrangement having the characteristics presented below in the characterising parts of the independent claims.
Some preferable embodiments of the present invention are described in the dependent claims.
Typical method according to the present invention for enzyme recovery in biofuel production process, comprises
- producing, by using liquid enzymes, an intermediate product mixture comprising a top phase comprising fatty acid esters and a bottom phase comprising glycerol,
- adding cationic polymer and an anionic surfactant or non-ionic surfactant to the intermediate product mixture,
- allowing an emulsion phase to form, the emulsion phase comprising liquid enzymes and
-separating the emulsion phase from the intermediate product mixture.
Now it has been surprisingly found that liquid enzymes are effectively concentrated to an emulsion phase, which is formed when an anionic or non-ionic surfactant and a cationic polyacrylamide are added to an intermediate product mixture in biofuel production process. The emulsion phase with liquid enzymes may be formed between the lighter top phase comprising fatty acid esters (FAE)
and heavier bottom phase comprising glycerol. The top phase is separated and transferred to biofuel processing and the bottom phase is separate and transferred to a further processing step. The emulsion phase, which comprises liquid enzymes, is easily separated from the top and bottom phase and the enzymes can be recycled back to process if desired.
The method of interaction is not yet fully understood, but it has been found out that a separable emulsion phase is formed when anionic or non-ionic surfactant and cationic polymer is added to the intermediate product mixture according to the present invention. The formed emulsion phase is quite distinct from the other phases of the intermediate mixture, i.e. FAE and glycerol phases. It has been observed that the liquid enzymes are concentrated to the emulsion phase and can be separated with it. In context of the present application the term "intermediate product mixture" is understood as a liquid mixture which comprise at least transesterification products, i.e. fatty acid esters (FAE); glycerol; liquid enzymes. The intermediate product mixture may further comprise water and/or residual alcohol. The invention is suitable for biofuel production by transesterification with liquid enzymes, such as lipases. In this context the term "liquid enzymes" is understood as enzymes that are free from attachment to surfaces of carrier elements, such as particles, and which are fully immersed into the reaction mixture. Liquid enzymes are fully dispersed in the reaction mixture, whereby they have good contact between the phases.
According to one preferred embodiment the separation of the emulsion phase comprising liquid enzymes from the bottom phase is performed by gravity sedimentation. Optionally, centrifugation may be used, but it is not necessary. The sedimentation time may vary between a few minutes up to a few hours, depending on the batch size.
The anionic or non-ionic surfactant and the cationic polymer may be added to the intermediate product mixture in any order. In other words, it is possible to first add the anionic or non-ionic surfactant and then the cationic polymer, or alternatively to add first the cationic polymer and then the anionic or non-ionic surfactant. According to an advantageous embodiment the anionic surfactant or non-ionic surfactant and the cationic polymer are added simultaneously to the intermediate product mixture.
The anionic or non-ionic surfactant may be added in any suitable amount. For example, the anionic surfactant may be added in amount up to 2800 ppm, normally in amount of 0.7 - 1400 ppm, preferably 140 - 420 ppm, more preferably 280 - 350 ppm, given as active agent. Anionic or non-ionic surfactant is usually used in form of a solution. Preferably an anionic surfactant and a cationic polymer are added to the intermediate product mixture.
The anionic surfactant may be selected from linear alkyl sulphates, branched alkyl sulphates, sulphosuccinates, linear alkyl benzene sulphonates, branched alkyl benzene sulphonates, alkylnaphthalenesulphonat.es and alkyldiphenyloxide disulphonates. According to one embodiment of the invention the anionic surfactant is sodium dioctyl sulphosuccinate.
The non-ionic surfactant may be selected from suitable ethoxylates.
The cationic polymer may be selected from a group comprising cationic polyacrylamide, polydiallyldimethylammonium chloride (poly-DADMAC), polyamine, cationic starch and chitosan. Preferably the cationic polymer is cationic polyacrylamide. Cationic polyacrylamide may be obtained by copolymerizing acrylamide with a cationic monomer or methacrylamide with a cationic monomer. The cationic monomer may be selected from the group consisting methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, 3-(methacrylamido) propyltrimethyl ammonium chloride, 3-
(acryloylamido) propyltrimethyl ammonium chloride, diallyldimethyl ammonium chloride, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, and similar monomers. According to one preferred embodiment of the invention cationic polyacrylamide is copolymer of acrylamide or methacrylamide with (meth)acryloyloxyethyltrimethyl ammonium chloride. Cationic polyacrylamide may also contain other monomers, as long as its net charge is cationic and it has an acrylamide/methacrylamide backbone. An acrylamide or methacrylamide based polymer may also be treated after the polymerisation to render it cationic, for example, by using Hofmann or Mannich reactions
Cationic polyacrylamide may have charge density of 0.15 - 4.0 meq/g, preferably 0.5 - 3.5 meq/g, more preferably 1 .5 - 3.0 meq/g. The cationic polymer, such as cationic polyacrylamide, may be added in any suitable amount, for example in amount up to 4000 ppm, normally in amount of 1 - 2000 ppm, preferably 200 - 600 ppm, more preferably 200 - 400 ppm, given as active agent. According to one embodiment of the invention the cationic polymer is used in form of dry powder.
The present invention is especially suitable for processes where biodiesel is produced by reacting glycerides (tri-, di-, mono-) with methanol in the presence of a liquid enzyme catalyst to produce an intermediate product mixture comprising fatty acid methyl esters (FAME) and glycerol.
The present invention is also suitable for biofuel production process, which comprises transesterification with liquid enzymes, such as lipases, from virgin vegetable oil feedstocks, such as soybean oil, or from waste feedstocks, such as waste vegetable oils, grease, animal fats.
EXPERIMENTAL
One embodiment of the invention is more closely described in the following non- limiting example.
Example 1
A batch of biodiesel was prepared in lab scale. The batch was a two-phase mixture composed of the clear top phase of fatty acid methyl ester (FAME), and of the emulsion phase at the bottom of the reaction vessel. After the separation of the top phase, about 1 litre of intermediate product mixture was left for lab trials.
Anionic surfactant comprising sodium dioctyl sulphosuccinate (KemFoamX 2970, Kemira Oyj) and cationic polyacrylamide flocculant (Superfloc C494, Kemira Oyj) were used in the experiments. Anionic surfactant was diluted to 10 weight-% aqueous solution and cationic polymer was diluted to 0.5 weight-% aqueous solution
The anionic surfactant and cationic polymer were added successively to 500 ml of intermediate product mixture upon fast mixing at room temperature. Fast mixing was continued for 5 minutes. After the mixing period, the mixture was allowed to settle for 30 minutes.
The results were evaluated visually, and the results are given in Table 1 . The dosages are given as amount of active substance.
Table 1 . Results of Example 1
It could be observed that for Sample 3 an effective separation of emulsion phase appeared already in 30 minutes. The emulsion phase was situated between a top phase comprising fatty acid methyl ester (FAME) and a bottom phase comprising glycerol. The bottom phase comprising glycerol could be easily separated from emulsion phase by using gravity settling. Correspondingly, the top phase comprising FAME can be separated for further processing for biodiesel. The emulsion phase comprising liquid enzymes can be recycled back to the process.
Even if the invention was described with reference to what at present seems to be the most practical and preferred embodiments, it is appreciated that the invention shall not be limited to the embodiments described above, but the invention is intended to cover also different modifications and equivalent technical solutions within the scope of the enclosed claims.
Claims
1 . Method for enzyme recovery in biofuel production process, the method comprising
- producing, by using liquid enzymes, an intermediate product mixture comprising a top phase comprising fatty acid esters and a bottom phase comprising glycerol, characterised in
- adding a cationic polymer and an anionic surfactant or non-ionic surfactant to the intermediate product mixture, allowing an emulsion phase to form, the emulsion phase comprising liquid enzymes and separating the emulsion phase from the intermediate product mixture.
2. Method according to claim 1 , characterised in forming the emulsion phase, which comprises liquid enzymes, between the top phase and the bottom phase.
3. Method according to claim 1 or 2, characterised in recycling the separated emulsion phase, which comprises liquid enzymes, back to the product step where the intermediate product mixture is produced.
4. Method according to any of preceding claims 1 - 3, characterised in performing the separation of the emulsion phase from the bottom phase by gravity sedimentation and/or by centrifugation.
5. Method according to any of preceding claims 1 - 4, characterised in adding an anionic surfactant and a cationic polymer to the intermediate product mixture.
6. Method according to claim 5, characterised in that the anionic surfactant is selected from linear alkyl sulphates, branched alkyl sulphates, sulphosuccinates, linear alkyl benzene sulphonates, branched alkyl benzene sulphonates, alkylnaphthalenesulphonat.es and alkyldiphenyloxide disulphonates..
7. Method according to claim 6, characterised in that the anionic surfactant is sodium dioctyl sulphosuccinate.
8. Method according to any of preceding claims 1 - 4, characterised in selecting non-ionic surfactant from ethoxylates.
9. Method according to any of preceding claims 1 - 8, characterised in adding anionic surfactant or non-ionic surfactant in amount of 0.7 - 1400 ppm, preferably 140 - 420 ppm, more preferably 280 - 350 ppm, given as active agent.
10. Method according to any of preceding claims 1 - 9, characterised in adding cationic polymer in amount up to 4000 ppm, preferably 1 - 2000 ppm, more preferably 200 - 600 ppm, even more preferably 200 - 400 ppm, given as active agent.
1 1 . Method according to any of preceding claims 1 - 10, characterised in that the cationic polymer is selected from group comprising cationic polyacrylamide, polydiailyldimethylammonium chloride (poly-DADMAC), polyamine, cationic starch and chitosan.
12. Method according to claim 1 1 , characterised in that the cationic polymer is cationic polyacrylamide.
13. Method according to claim 12, characterised in that cationic polyacrylamide has charge density of 0.15 - 4.0 meq/g, preferably 0.5 - 3.5 meq/g, more preferably 1 .5 - 3.0 meq/g.
14. Method according to any of preceding claims 1 - 13, characterised in that the cationic polymer is added simultaneously with the anionic surfactant to the intermediate product mixture.
15. Method according to any of preceding claims 1 - 14, characterised in
- separating the top phase and transferring it to biofuel processing, and
- separating the bottom phase and transferring it to a further processing step.
16. Method according to any of preceding claims 1 - 15, characterised in the biofuel production process comprises transesterification with liquid enzymes, such as lipases, from virgin vegetable oil feedstocks, such as soybean oil, or from waste feedstocks, such as waste vegetable oils, grease, animal fats.
17. Method according to any of preceding claims 1 - 16, characterised in the biofuel production process where biodiesel is produced by reacting glycerides, such as tri- , di-, monoglycerides, with methanol in the presence of a liquid enzyme catalyst to produce an intermediate product mixture comprising fatty acid methyl esters and glycerol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20136199 | 2013-11-29 | ||
| FI20136199A FI125311B (en) | 2013-11-29 | 2013-11-29 | Process for enzyme recovery in biofuel production |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998033979A1 (en) * | 1997-02-05 | 1998-08-06 | Akzo Nobel N.V. | Sizing of paper |
| WO1998033980A1 (en) * | 1997-02-05 | 1998-08-06 | Akzo Nobel N.V. | Aqueous dispersions of hydrophobic material |
| CN101418322A (en) * | 2008-12-11 | 2009-04-29 | 清华大学 | Method for preparing biodiesel through catalysis of renewable lipin by lipase recovered by membrane |
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- 2013-11-29 FI FI20136199A patent/FI125311B/en not_active IP Right Cessation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998033979A1 (en) * | 1997-02-05 | 1998-08-06 | Akzo Nobel N.V. | Sizing of paper |
| WO1998033980A1 (en) * | 1997-02-05 | 1998-08-06 | Akzo Nobel N.V. | Aqueous dispersions of hydrophobic material |
| CN101418322A (en) * | 2008-12-11 | 2009-04-29 | 清华大学 | Method for preparing biodiesel through catalysis of renewable lipin by lipase recovered by membrane |
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| FI125311B (en) | 2015-08-31 |
| FI20136199A (en) | 2015-05-30 |
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