EP3922707A1 - Reduction of foul odors in bioethanol - Google Patents
Reduction of foul odors in bioethanol Download PDFInfo
- Publication number
- EP3922707A1 EP3922707A1 EP21178454.1A EP21178454A EP3922707A1 EP 3922707 A1 EP3922707 A1 EP 3922707A1 EP 21178454 A EP21178454 A EP 21178454A EP 3922707 A1 EP3922707 A1 EP 3922707A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- bioethanol
- additive
- range
- additive mixture
- 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.)
- Pending
Links
- 235000019645 odor Nutrition 0.000 title claims description 58
- 239000000654 additive Substances 0.000 claims abstract description 123
- 230000000996 additive effect Effects 0.000 claims abstract description 123
- 239000000203 mixture Substances 0.000 claims abstract description 85
- 239000007800 oxidant agent Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims description 65
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 19
- 239000003085 diluting agent Substances 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000003398 denaturant Substances 0.000 claims description 10
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 10
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 8
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 7
- 229940045872 sodium percarbonate Drugs 0.000 claims description 7
- JADAAITZSTVOLP-UHFFFAOYSA-N CCC(C)CC(=O)CC.CCC(=O)CCC(C)C Chemical compound CCC(C)CC(=O)CC.CCC(=O)CCC(C)C JADAAITZSTVOLP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005844 Thymol Substances 0.000 claims description 5
- 229960000790 thymol Drugs 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- VWTINHYPRWEBQY-UHFFFAOYSA-N denatonium Chemical compound [O-]C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C[N+](CC)(CC)CC(=O)NC1=C(C)C=CC=C1C VWTINHYPRWEBQY-UHFFFAOYSA-N 0.000 claims description 4
- 229960001610 denatonium benzoate Drugs 0.000 claims description 4
- -1 ethane peroxy acid Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 235000011118 potassium hydroxide Nutrition 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
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- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
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- 235000021536 Sugar beet Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
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- 230000000740 bleeding effect Effects 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
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- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 239000013026 undiluted sample Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
- C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
-
- C—CHEMISTRY; METALLURGY
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
- C10L1/1258—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof hydrogen peroxide, oxygenated water
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
-
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1857—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2227—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond urea; derivatives thereof; urethane
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
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- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
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- C—CHEMISTRY; METALLURGY
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- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/08—Inhibitors
- C10L2230/088—Inhibitors for inhibiting or avoiding odor
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- C—CHEMISTRY; METALLURGY
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- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
Definitions
- the present invention relates to a use of an additive mixture for reducing off-odors in bioethanol.
- the present invention further relates to a method for reducing off-odors in bioethanol comprising an additive mixture and a product produced by the method for reducing off-odors in bioethanol.
- Bioethanol is produced exclusively from biological waste or biological matter, such as sugar beet, potatoes, corn, grain, wood and straw, through fermentation, also known as alcoholic fermentation, using enzymes and microorganisms. Bioethanol has been used for biofuels, such as E10 and E5, for use in Otto combustion engines to replace mineral fuels since 2004. Bioethanol burns without soot, since only water and carbon dioxide are produced as waste products. Bioethanol is also used in the cosmetics industry.
- bioethanol Compared to conventional mineral fuels such as gasoline, bioethanol has a higher octane number, is almost sulfur-free and biodegradable, which makes it an environmentally friendly and, above all, renewable alternative to conventional mineral fuels.
- Bioethanol is not only a renewable raw material, it also enables it to be produced independently of oil deposits. Because it is manufactured through fermentation using enzymes and microorganisms, the commercially available bioethanol for biofuels has an unpleasant odor of burnt rubber and stables, which becomes even more intense when it evaporates. In anaerobic fermentation, in addition to bioethanol, hydrogen sulfide, for example, is produced, which contributes to the unpleasant odor.
- Bioethanol is primarily intended to be used as fuel, which means that an unpleasant odor can be neglected. When used as petrol, this off-smell is not a major problem, but it is in other bioethanol applications.
- DE 10 2012 024 111 A1 discloses a method for odor treatment of organic substrates, in which an odor treatment substance formed on the basis of iron chlorides is introduced or introduced into a bio-substrate.
- CN 103160336 discloses a bio-alcohol oil based on edible oil waste oil esters comprising a deodorant, the deodorant being camphor or ammonia.
- EP 1 884 555 A2 discloses a mineral oil wherein the mineral oil odor is masked. Masking mineral oil odor is understood to mean the complete or partial covering of the mineral oil maldor by a fragrance or a mixture of odorous substances, so that the sensory maldor impression is reduced or covered.
- the object of the present invention is to provide a bioethanol which does not have any unpleasant offensive odor.
- This object is achieved according to the invention by using an additive mixture comprising at least one alkaline additive and at least one oxidizing agent for reducing off-odors in bioethanol, more preferably using a bioethanol treated with an additive mixture comprising at least one alkaline additive and at least one oxidizing agent for reducing off-odors as Cleaning agents and disinfectants or in the cosmetics industry.
- the purest fraction is called neutral ethanol and has a purity of at least 99%.
- Neutral ethanol is used in the manufacture of alcoholic beverages and medical applications.
- Bioethanol which is to be used for biofuels, does not need such a high degree of purity. This means that the proportion of water, sulfur-containing or other compounds in these fractions is higher.
- this In order to be able to use cheaper bioethanol as a basis, for example for cosmetics or for disinfectants of any kind, this must be treated to remove the odor-intensive compounds, in particular Hydrogen sulfide, to neutralize. Further purification by distillation would not lead to a complete purification, but in turn to more heavily contaminated fractions and purer fractions. Such a distillation is also energy-intensive and therefore cost-intensive.
- the bioethanol to be treated according to the invention preferably has a purity of about 98% and higher.
- the additive mixture according to the invention reduces the unpleasant offensive odor of the bioethanol to be treated.
- the odor reduction is brought about by a preferably two-stage reaction in bioethanol in order to break down the odor-forming compounds, in particular hydrogen sulfide.
- the additive mixture comprises several components, including according to the invention at least one alkaline additive and at least one oxidizing agent, more preferably at least one triol and / or at least one denaturing agent, which are described in more detail below.
- the additive mixture comprises at least one oxidizing agent.
- the at least one oxidizing agent is preferably selected from a group comprising hydrogen peroxide, ethane peroxy acid, sodium percarbonate, urea peroxohydrate or a mixture of these.
- An at least 10%, preferably at least 75%, aqueous solution of the at least one oxidizing agent is preferably used.
- a 30% hydrogen peroxide solution has 9.8 mol / l hydrogen peroxide.
- the at least one oxidizing agent reacts with the odorous compounds present in the bioethanol to be treated.
- hydrogen sulfide H 2 S reacts with hydrogen peroxide to form sulfuric acid.
- the sulfuric acid formed is further converted by the at least one alkaline additive.
- the at least one oxidizing agent is preferably in a range from about 1% by weight to about 80% by weight, more preferably in a range from about 1.6% by weight to about 75% by weight, based on the total amount the additive mixture, comprised
- the additive mixture comprises at least one alkaline additive.
- the at least one alkaline additive is preferably selected from a group comprising potassium hydroxide, sodium hydroxide, primary amines, secondary amines, tertiary amines, sodium carbonate, potassium carbonate or a mixture of these.
- a 20% strength potassium hydroxide solution has 4.21 mol / l potassium hydroxide.
- a 20% sodium hydroxide solution has 6.09 mol / l sodium hydroxide.
- the at least one alkaline additive reacts with the compounds generated by the at least one oxidizing agent in the bioethanol to be treated. If, for example, potassium hydroxide is used, the reaction with sulfuric acid formed from hydrogen sulfide produces potassium sulfate K 2 SO 4 . As a result of the reaction, which can preferably be carried out in two stages, the odor-forming compounds are converted into stable and soluble ions. If an excess of the at least one alkaline additive is used, the resulting salt can precipitate. According to the invention, the precipitation of the resulting salt is preferably prevented by adjusting the pH.
- the at least one alkaline additive is preferably in an amount in a range from about 1% by weight to about 50% by weight, particularly preferably in a range from about 1.6% by weight to about 45% by weight, based on the total amount of the additive mixture, comprised by this.
- the additive mixture preferably comprises at least one triol.
- the at least one triol is more preferably selected from a group comprising glycerol.
- the at least one triol is preferably comprised in a range from about 5% by weight to about 25% by weight, more preferably in a range from about 8% by weight to about 24% by weight, based on the total amount of Additive mixture.
- the additive mixture preferably comprises at least one denaturant.
- the at least one denaturant is more preferably selected from a group comprising butanone, diethyl phthalate, thymol, isopropanol, tertiary butanol, denatonium benzoate, methyl ethyl ketone, methyl isopropyl ketone, ethyl isoamyl ketone (5-methyl-3-heptanone) and / or pyridine bases. Since the at least one oxidizing agent can react with the denaturing agent already added to the bioethanol, at least one denaturing agent must be added again to the treated bioethanol after odors have been removed by the additive mixture.
- the denaturants which can be used according to the invention preferably have a boiling point similar to that of ethanol, in order to prevent separation of the same when a distillation may still be carried out.
- Another selection criterion of the at least one denaturing agent is an intense, unpleasant taste at a low concentration in order to prevent the use of bioethanol without taxation for alcoholic beverages.
- the at least one denaturant is preferably in a range from about 0.0005% by weight to about 30% by weight, more preferably in a range from about 0.001% by weight to about 25% by weight, based on the total amount the additive mixture, comprised of this.
- the term "approximately” is used in connection with values or value ranges, this is to be understood as a tolerance range which the person skilled in the art in this field considers normal, in particular a tolerance range of ⁇ 20%, preferably ⁇ 10%, more preferably ⁇ 5%, even more preferably ⁇ 3%, are provided.
- the lower limit values claimed in the present invention and the upper limit values of the various ranges, in particular the weight percentage ranges, but not limited thereto, can be combined with one another to define new ranges.
- percent by weight or% by weight in relation to the components consisting of the claimed method and the claimed use, the term percent by weight relates to the amount of one or more components in relation to the total amount of the components used, usually the Additive mixture or the solution obtained in the process according to the invention, unless expressly stated otherwise.
- wt .-% is used throughout the present invention as an abbreviation for percent by weight, unless otherwise specified.
- bioethanol is treated with an offensive odor. That to be treated Bioethanol is in an amount in the range from about 20% by weight to about 97% by weight, even more preferably in an amount in a range from about 50% by weight to about 85% by weight, based on the total amount the solution obtained.
- the solution obtained comprises the bioethanol to be treated, the at least one diluent and the above-described additive mixture according to the invention.
- a diluent is added to the bioethanol to be treated in process step a).
- the at least one diluent is preferably water.
- the at least one diluent is more preferably tap water or deionized water.
- Deionized water is water without the salts found in spring and tap water, which are dissolved as anions and cations, and is used in chemistry and biology as a solvent and sometimes also as a cleaning agent.
- Process step a) diluting the bioethanol to be treated is preferably carried out before process step b) adding an additive mixture.
- the at least one diluent is preferably in a range from about 3% by weight to about 80% by weight and more preferably in a range from about 5% by weight to about 50% by weight, based on the total amount of the solution obtained , covered by this.
- the ratio between the amount of water and the amount of bioethanol is preferably in a range from about 0.2 to about 0.9, and even more preferably in a range from about 0.5 to about 0.8.
- the ratio between the amount of water and the amount of bioethanol is tailored to the use of the solution obtained.
- the previously described additive mixture according to the invention is added to the bioethanol to be treated in process step b).
- the additive mixture is added sequentially.
- the at least one oxidizing agent is preferably added to the bioethanol to be treated first, and then the at least one alkaline additive; alternatively, the oxidizing agent and the alkaline additive can also be added in reverse order or at the same time, depending on the compounds used .
- the at least one oxidizing agent is preferably in an amount in a range from about 0.01% by weight to about 8% by weight, particularly preferably in a range from about 0.02% by weight to about 7% by weight, based on the total amount of the solution obtained .
- the at least one alkaline additive is added after the addition of the at least one oxidizing agent.
- the pH of the solution obtained is preferably set in a range from about 7 to about 13 by means of the alkaline additive.
- a sample of the solution obtained is separated off and diluted to such an extent that a water content of at least 50% by weight is reached.
- the pH value is then measured using a WTW 3310 pH meter with the SenTix 81 pH electrode manufactured by WTW at a temperature of 20 ° C.
- the at least one alkaline additive is preferably in an amount in a range from about 0.01% by weight to about 5% by weight, particularly preferably in a range from about 0.02% by weight to about 3% by weight. %, based on the total amount of the solution obtained, comprised of this.
- the at least one denaturing agent is preferably added after the at least one oxidizing agent.
- the one denaturing agent is preferably added to the mixture obtained after a possible excess of the at least one oxidizing agent has been broken down.
- the at least one denaturant is preferably in an amount in a range from about 0.0001% by weight to about 5% by weight, particularly preferably in a range from about 0.0002% by weight to about 4% by weight , based on the total amount of the solution obtained, comprised by this.
- the addition of at least one triol is preferably included in a further step.
- the at least one triol is preferably in an amount in a range from about 0.01% by weight to about 5% by weight, particularly preferably in a range from about 0.1% by weight to about 4% by weight , based on the total amount of the solution obtained from this.
- the addition of at least one reducing agent is preferred.
- the at least one reducing agent is more preferably selected from a group comprising ascorbic acid, sodium ascorbate, sulfites, thiosulfates, catalase or a mixture this.
- An excess of the at least one oxidizing agent is preferably neutralized by adding at least one reducing agent. By neutralizing the excess oxidizing agent, the solution obtained, also called treated bioethanol, is stable in storage.
- the at least one reducing agent is added dropwise to the resulting solution until there is no longer any excess oxidizing agent.
- the content of the at least one oxidizing agent is determined by a commercially available peroxide test, such as peroxide test sticks MQUANT ® from Merck KGaA Germany. This determination of the content is repeated during the addition of the at least one reducing agent until the peroxide test no longer detects any oxidizing agent.
- the sequential addition has the advantage of preventing the individual components of the additive mixture from reacting with one another.
- the additive mixture is preferably in an amount in a range from about 0.001% by weight to about 20% by weight, more preferably in a range from about 0.005% by weight to about 17.5% by weight, based on the Total amount of the solution obtained, added to this.
- the solution obtained is homogenized in process step c).
- the homogenization can preferably be carried out during and after process steps a) and b).
- the homogenization according to the invention comprises, for example, stirring and / or shaking the solution obtained.
- Room temperature is the average room air temperature.
- the room temperature is preferably in a range from about 18 ° C to about 25 ° C, more preferably in a range from about 20 ° C to about 23 ° C.
- the odor determination of the solution obtained within the meaning of the present invention is preferably carried out by at least two people who determine the odor independently of one another.
- the odor determination is carried out in a well-ventilated room.
- the samples are stored in tightly closed vessels, which must be odorless when closed.
- the samples are assessed at room temperature. With a pipette, 3 to 4 drops are placed on a surface heated to 30 ° C and passed into a thin film.
- the olfactory assessment of the evaporating sample film is assessed olfactorily by gently fanning the odor.
- the vessel is tightly closed again after each sample. As a comparison, this process is carried out immediately before the sample or after the sample, once with untreated bioethanol and once with pure ethanol. These steps can be repeated.
- the evaluation scheme is divided into odor categories with key figures, as shown in Table 1 below.
- the sample to be assessed is divided by the individual into one of the odor categories and the decrease in the unpleasant odor is quantified with the code number 10 until it disappears completely and a transition to a neutral ethanol odor with a slightly fruity ester note is quantified with the code number 1.
- the odor determination is carried out at several points in time. It is preferred to determine the odor at the time 0 hours, directly after the addition of the alkaline additive and / or oxidizing agent, and after the components have reacted the additive mixture according to the invention carried out with the bioethanol to be treated.
- the odor determination is carried out after the completion of method step c) of the aforementioned method according to the invention, which corresponds to the time 0 hours.
- the reaction of the components of the additive mixture is usually complete after 24 hours at the latest. A final odor determination is therefore preferably carried out 24 hours after the end of process step c).
- the present invention further relates to a product produced by the aforementioned method according to the invention.
- the product according to the invention is the solution obtained, which in the present invention is also referred to as odorless treated bioethanol.
- the odor-free treated bioethanol is preferably used as a basis for cleaning agents and disinfectants or in the cosmetics industry.
- An exemplary use according to the invention of an additive mixture preferably comprises at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight .-%, based on the total amount of the additive mixture, to reduce bad odors in bioethanol.
- An exemplary use according to the invention of an additive mixture comprises even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the total amount of the additive mixture, to reduce bad odors in bioethanol, the at least one oxidizing agent being selected from a group comprising hydrogen peroxide, ethane peroxy acid, sodium percarbonate, urea peroxohydrate or a mixture of these.
- An exemplary use according to the invention of an additive mixture encompasses even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the Total amount of the additive mixture to reduce off-odors in bioethanol, the at least one alkaline additive being selected from a group comprising potassium hydroxide, sodium hydroxide, primary amines, secondary amines, tertiary amines, sodium carbonate, potassium carbonate or a mixture of these.
- An exemplary use according to the invention of an additive mixture comprises even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the total amount of the additive mixture, for reducing off-odors in bioethanol, the additive mixture comprising at least one triol, the at least one triol preferably being selected from a group comprising glycerol and the at least one triol preferably being in a range from about 5% by weight to about 25% by weight, based on the total amount of the additive mixture.
- An exemplary use according to the invention of an additive mixture comprises even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the total amount of the additive mixture, for reducing off-odors in bioethanol, the additive mixture further preferably comprising at least one denaturing agent, the at least one denaturing agent being selected from a group comprising butanone, diethyl phthalate, thymol, isopropanol, and tertiary butanol , Denatonium benzoate, methyl ethyl ketone, methyl isopropyl ketone, ethyl isoamyl ketone (5-methyl-3-heptanone) and / or pyridine bases, and wherein the at least one denaturant is preferably comprised in a range from about 0.0005% by weight to about 30% by weight , based
- An exemplary use according to the invention of an additive mixture preferably comprises at least one alkaline additive in an amount in a range of about 1% by weight up to about 45% by weight and at least one oxidizing agent in a range from about 1% by weight to about 75% by weight, based on the total amount of the additive mixture, to reduce bad odors in bioethanol.
- An exemplary use according to the invention of an additive mixture preferably comprises at least one alkaline additive in an amount in a range from about 1.6% by weight to about 45% by weight and at least one oxidizing agent in a range from about 1.6% by weight up to about 75% by weight, based on the total amount of the additive mixture, to reduce off-smells in bioethanol.
- Bioethanol with a purity of 98.7% by volume was used.
- Deionized water was used as a diluent.
- Glycerin with a purity of 86.5% was also used.
- Aqueous sodium hydroxide solution was used as an alkaline additive in a concentration of 6.09 mol / l, which corresponds to a 20% solution.
- Aqueous potassium hydroxide solution was used as an alkaline additive with a concentration of 4.21 mol / l, which corresponds to a 20% solution.
- a hydrogen peroxide solution with a concentration of 9.80 mol / l, which corresponds to a 30% solution, and with a pH value of 3.5 pH at 20 ° C.
- Bioethanol was placed in a sealable reaction vessel at room temperature. Deionized water was added to the submitted bioethanol. After the bioethanol-water solution was homogenized, hydrogen peroxide was added. After all of the hydrogen peroxide had been added, the alkaline additive and, if necessary, further components, such as glycerine, were added. The resulting solution was homogenized by stirring. The first odor determination according to the aforementioned method and a pH value measurement by a pH meter WTW 3310 with the pH electrode SenTix 81 at 20 ° C was carried out at the time 0 hours. After 24 hours, a second odor determination and pH value measurement were carried out.
- composition of the solutions of working examples A1 to A7 according to the invention and a comparative example A8 are shown in Table 2 below, the amounts being given in% by weight, based on the total amount of the composition.
- Table 2 Composition of the solutions of working examples A1 to A7 according to the invention and comparative example A8.
- the embodiment example A1 with 20% potassium hydroxide solution and 30% hydrogen peroxide shows a complete odor reduction after 24 hours.
- the exemplary embodiments A2 and A3 with potassium hydroxide solution, glycerine and hydrogen peroxide, like A1 have a complete odor reduction with a hydrogen peroxide content of 0.1% by weight and 4.63% by weight.
- the off-odor can thus be completely reduced by adding hydrogen peroxide in a range from 0.1% by weight to 5% by weight of the 30% strength hydrogen peroxide solution used.
- the off-odor in exemplary embodiment A4 is reduced to 1 after 24 hours.
- a low hydrogen peroxide content and a low potassium hydroxide content according to A4 indicate a constant reduction in odor, even at a slightly lower pH value.
- A5 has no off-odor after 24 hours, which suggests that caustic soda can be used as an alternative to caustic potash.
- Exemplary embodiment A6 with ethanolamine as the alkaline additive still had a slight off-odor "slightly acidic like vinegar" corresponding to the odor index 3 after 24 hours.
- ethanolamine as an alkaline additive, is somewhat inferior to potassium hydroxide and sodium hydroxide solution with the same hydrogen peroxide content, but nevertheless delivers good results.
- the exemplary embodiment A7 with sodium percarbonate as the oxidizing agent shows comparable results to the exemplary embodiment A3 with hydrogen peroxide.
- Comparative example A8 with an odor index of 6 after 24 hours does not show a complete reduction in the off-odor.
- the pH of Comparative Example A8 is 3 pH, which is likely to explain the insufficient reduction in the off-odor of the bioethanol and the lack of the alkaline additive.
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- Detergent Compositions (AREA)
Abstract
Die vorliegende Erfindung betrifft eine Verwendung einer Additivmischung umfassend mindestens einen alkalischen Zusatzstoff und mindestens ein Oxidationsmittel zur Minderung von Fehlgerüchen in Bioethanol. Weiter betrifft die vorliegende Erfindung ein Verfahren zur Minderung von Fehlgerüchen in Bioethanol umfassend eine Additivmischung als auch ein Produkt hergestellt durch das Verfahren zur Minderung von Fehlgerüchen in Bioethanol.The present invention relates to the use of an additive mixture comprising at least one alkaline additive and at least one oxidizing agent for reducing off-odors in bioethanol. The present invention further relates to a method for reducing off-odors in bioethanol comprising an additive mixture and also a product produced by the method for reducing off-odors in bioethanol.
Description
Die vorliegende Erfindung betrifft eine Verwendung einer Additivmischung zur Minderung von Fehlgerüchen in Bioethanol. Weiter betrifft die vorliegende Erfindung ein Verfahren zur Minderung von Fehlgerüchen in Bioethanol umfassend eine Additivmischung als auch ein Produkt hergestellt durch das Verfahren zur Minderung von Fehlgerüchen in Bioethanol.The present invention relates to a use of an additive mixture for reducing off-odors in bioethanol. The present invention further relates to a method for reducing off-odors in bioethanol comprising an additive mixture and a product produced by the method for reducing off-odors in bioethanol.
Bioethanol wird ausschließlich aus biologischen Abfällen oder biologischer Masse, beispielsweise Zuckerrüben, Kartoffeln, Mais, Getreide, Holz und Stroh, durch Fermentation, auch alkoholische Gärung genannt, unter Einsatz von Enzymen und Mikroorganismen hergestellt. Seit 2004 wird Bioethanol für Biokraftstoffe, wie E10 und E5, zur Verwendung in Otto-Verbrennungsmotoren eingesetzt, um mineralische Kraftstoffe zu ersetzen. Bioethanol verbrennt ohne zu Rußen, da nur Wasser und Kohlenstoffdioxid als Abfallprodukte entstehen. Bioethanol wird auch in der Kosmetikindustrie verwendet.Bioethanol is produced exclusively from biological waste or biological matter, such as sugar beet, potatoes, corn, grain, wood and straw, through fermentation, also known as alcoholic fermentation, using enzymes and microorganisms. Bioethanol has been used for biofuels, such as E10 and E5, for use in Otto combustion engines to replace mineral fuels since 2004. Bioethanol burns without soot, since only water and carbon dioxide are produced as waste products. Bioethanol is also used in the cosmetics industry.
Bioethanol hat im Vergleich zu konventionellen mineralischen Ottokraftstoffen, wie Benzin, eine höhere Oktanzahl, ist nahezu schwefelfrei und biologisch abbaubar, was es zu einer umweltfreundlichen und vor allem nachwachsenden Alternative zu konventionellen mineralischen Ottokraftstoffen macht. Nicht nur ist Bioethanol ein nachwachsender Rohstoff, sondern ermöglicht es, diesen unabhängig von Ölvorkommen herzustellen. Aufgrund der Herstellungsweise über die Fermentation mittels Enzyme und Mikroorganismen weist der handelsübliche Bioethanol für Biokraftstoffe einen unangenehmen Fehlgeruch nach verbranntem Gummi und Stall, welcher bei Verdunstung noch intensiver wird, auf. Bei der anaeroben Fermentation entsteht neben dem Bioethanol zum Beispiel Schwefelwasserstoff, welcher zu dem unangenehmen Fehlgeruch beiträgt. Trotz der üblichen Aufreinigung des Bioethanols durch Destillation ist auch ein gewisser Anteil des Schwefelwasserstoffs und auch sonstige Verbindungen weiterhin im aufgereinigtem Bioethanol gelöst. Bioethanol ist vorrangig dafür bestimmt als Kraftstoff verwendet zu werden, wodurch ein unangenehmer Fehlgeruch zu vernachlässigen ist. Bei der Verwendung als Ottokraftstoff stellt dieser Fehlgeruch kein großes Problem dar, aber in anderen Anwendungen von Bioethanol schon.Compared to conventional mineral fuels such as gasoline, bioethanol has a higher octane number, is almost sulfur-free and biodegradable, which makes it an environmentally friendly and, above all, renewable alternative to conventional mineral fuels. Bioethanol is not only a renewable raw material, it also enables it to be produced independently of oil deposits. Because it is manufactured through fermentation using enzymes and microorganisms, the commercially available bioethanol for biofuels has an unpleasant odor of burnt rubber and stables, which becomes even more intense when it evaporates. In anaerobic fermentation, in addition to bioethanol, hydrogen sulfide, for example, is produced, which contributes to the unpleasant odor. Despite the usual purification of bioethanol by distillation, a certain proportion of the hydrogen sulfide and other compounds are still dissolved in the purified bioethanol. Bioethanol is primarily intended to be used as fuel, which means that an unpleasant odor can be neglected. When used as petrol, this off-smell is not a major problem, but it is in other bioethanol applications.
Damit ist aus dem Stand der Technik bekannt, eine Geruchsbehandlung von biologischen Ölen und Mineralölen durch Zugabe von Riechstoffen, wie Kampfer, etherischen Ölen, oder Katalysatoren, wie Ferrocen und Eisenchlorid, vorzunehmen. Auch ein mehrfaches Reinigen durch Destillation kann zur Beseitigung von Fehlgeruch geeignet sein. Hierbei handelt es sich jedoch um teure, energieaufwändige und zeitraubende Methoden.It is thus known from the prior art to carry out an odor treatment of biological oils and mineral oils by adding odorous substances such as camphor, essential oils, or catalysts such as ferrocene and iron chloride. Repeated cleaning by distillation can also be used to remove off-smells. However, these are expensive, energy-consuming and time-consuming methods.
Aufgabe der vorliegenden Erfindung ist es, ein Bioethanol zur Verfügung zu stellen, welches keinen unangenehmen Fehlgeruch aufweist.The object of the present invention is to provide a bioethanol which does not have any unpleasant offensive odor.
Diese Aufgabe wird erfindungsgemäß gelöst durch eine Verwendung einer Additivmischung umfassend mindestens einen alkalischen Zusatzstoff und mindestens ein Oxidationsmittel zur Minderung von Fehlgerüchen in Bioethanol, weiter bevorzugt eine Verwendung eines mit einer Additivmischung umfassend mindestens einen alkalischen Zusatzstoff und mindestens ein Oxidationsmittel zur Minderung von Fehlgerüchen behandelten Bioethanols als Reinigungs- und Desinfektionsmittel oder in der Kosmetikindustrie.This object is achieved according to the invention by using an additive mixture comprising at least one alkaline additive and at least one oxidizing agent for reducing off-odors in bioethanol, more preferably using a bioethanol treated with an additive mixture comprising at least one alkaline additive and at least one oxidizing agent for reducing off-odors as Cleaning agents and disinfectants or in the cosmetics industry.
Bei der Reinigung des Bioethanols nach dessen Herstellung entstehen unterschiedlich reine Fraktionen. Die reinste Fraktion wird Neutralethanol genannt und besitzt eine Reinheit von mindestens 99 %. Neutralethanol wird zur Herstellung von alkoholischen Getränken und medizinischen Anwendungen verwendet. Bioethanol, der für Biokraftstoffe verwendet werden soll, braucht keine solch hohe Reinheit. Somit ist der Anteil von Wasser, schwefelhaltigen oder sonstigen Verbindungen in diesen Fraktionen höher. Um kostengünstigeres Bioethanol als Basis z.B. für Kosmetika oder für Desinfektionsmittel gleich welcher Art verwenden zu können, muss dieser behandelt werden, um die geruchsintensiven Verbindungen, insbesondere Schwefelwasserstoff, zu neutralisieren. Ein weiteres Reinigen durch Destillation würde nicht zu einer kompletten Aufreinigung führen, sondern wiederum zu stärker verunreinigten Fraktionen und reineren Fraktionen. Eine solche Destillation ist außerdem energetisch aufwändig und damit kostenintensiv. Der erfindungsgemäß zu behandelnde Bioethanol hat bevorzugt eine Reinheit von etwa 98 % und höher.When the bioethanol is purified after its production, fractions of different purity are created. The purest fraction is called neutral ethanol and has a purity of at least 99%. Neutral ethanol is used in the manufacture of alcoholic beverages and medical applications. Bioethanol, which is to be used for biofuels, does not need such a high degree of purity. This means that the proportion of water, sulfur-containing or other compounds in these fractions is higher. In order to be able to use cheaper bioethanol as a basis, for example for cosmetics or for disinfectants of any kind, this must be treated to remove the odor-intensive compounds, in particular Hydrogen sulfide, to neutralize. Further purification by distillation would not lead to a complete purification, but in turn to more heavily contaminated fractions and purer fractions. Such a distillation is also energy-intensive and therefore cost-intensive. The bioethanol to be treated according to the invention preferably has a purity of about 98% and higher.
Die erfindungsgemäße Additivmischung mindert den unangenehmen Fehlgeruch des zu behandelnden Bioethanols. Die Geruchsminderung wird durch eine bevorzugt zweistufige Reaktion in Bioethanol herbeigeführt, um die geruchsbildenden Verbindungen, insbesondere Schwefelwasserstoff, abzubauen. Zur Minderung des Fehlgeruchs umfasst die Additivmischung mehrere Komponenten, darunter erfindungsgemäß mindestens einen alkalischen Zusatzstoff und mindestens ein Oxidationsmittel, weiter bevorzugt mindestens ein Triol und/oder mindestens ein Vergällungsmittel, die im Folgenden näher beschrieben werden.The additive mixture according to the invention reduces the unpleasant offensive odor of the bioethanol to be treated. The odor reduction is brought about by a preferably two-stage reaction in bioethanol in order to break down the odor-forming compounds, in particular hydrogen sulfide. To reduce the offensive odor, the additive mixture comprises several components, including according to the invention at least one alkaline additive and at least one oxidizing agent, more preferably at least one triol and / or at least one denaturing agent, which are described in more detail below.
Erfindungsgemäß ist von der Additivmischung mindestens ein Oxidationsmittel umfasst. Bevorzugt ist das mindestens eine Oxidationsmittel ausgewählt aus einer Gruppe umfassend Wasserstoffperoxid, Ethanperoxosäure, Natriumpercarbonat, Harnstoffperoxohydrat oder einer Mischung dieser. Bevorzugt wird eine mindestens 10 %ige bis bevorzugt mindestens 75 %ige wässrige Lösung des mindestens einen Oxidationsmittels verwendet. Beispielsweise weist eine 30 %ige Wasserstoffperoxid-Lösung 9,8 mol/l Wasserstoffperoxid auf. Das mindestens eine Oxidationsmittel reagiert mit den im zu behandelnden Bioethanol vorhandenen geruchsbildenden Verbindungen. Beispielsweise reagiert Schwefelwasserstoff H2S mit Wasserstoffperoxid zu Schwefelsäure. Die entstandene Schwefelsäure wird durch den mindestens einen alkalischen Zusatzstoff weiter umgesetzt. Bevorzugt ist das mindestens eine Oxidationsmittel in einem Bereich von etwa 1 Gew.-% bis etwa 80 Gew.-%, weiter bevorzugt in einem Bereich von etwa 1,6 Gew.-% bis etwa 75 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, von dieser umfasst.According to the invention, the additive mixture comprises at least one oxidizing agent. The at least one oxidizing agent is preferably selected from a group comprising hydrogen peroxide, ethane peroxy acid, sodium percarbonate, urea peroxohydrate or a mixture of these. An at least 10%, preferably at least 75%, aqueous solution of the at least one oxidizing agent is preferably used. For example, a 30% hydrogen peroxide solution has 9.8 mol / l hydrogen peroxide. The at least one oxidizing agent reacts with the odorous compounds present in the bioethanol to be treated. For example, hydrogen sulfide H 2 S reacts with hydrogen peroxide to form sulfuric acid. The sulfuric acid formed is further converted by the at least one alkaline additive. The at least one oxidizing agent is preferably in a range from about 1% by weight to about 80% by weight, more preferably in a range from about 1.6% by weight to about 75% by weight, based on the total amount the additive mixture, comprised of this.
Erfindungsgemäß ist von der Additivmischung mindestens ein alkalischer Zusatzstoff umfasst. Bevorzugt ist der mindestens eine alkalische Zusatzstoff ausgewählt aus einer Gruppe umfassend Kaliumhydroxid, Natriumhydroxid, primäre Amine, sekundäre Amine, tertiäre Amine, Natriumcarbonat, Kaliumcarbonat oder einer Mischung dieser. Bevorzugt wird eine mindestens 10 %ige bis bevorzugt 50% ige wässrige Lösung des mindestens einen alkalischen Zusatzstoffes, insbesondere von Natriumhydroxid und Kaliumhydroxid, verwendet. Beispielsweise weist eine 20 %ige Kaliumlauge 4,21 mol/l Kaliumhydroxid auf. Beispielsweise weist eine 20%igeNatriumlauge 6,09 mol/l Natriumhydroxid auf. Der mindestens eine alkalische Zusatzstoff reagiert mit den durch das mindestens eine Oxidationsmittel erzeugten Verbindungen in dem zu behandelnden Bioethanol. Wird zum Beispiel Kaliumhydroxid eingesetzt, so entsteht bei der Reaktion mit aus Schwefelwasserstoff gebildeter Schwefelsäure Kaliumsulfat K2SO4. Durch die Reaktion, die bevorzugt zweistufig durchgeführt werden kann, werden die geruchsbildenden Verbindungen in stabile und lösliche Ionen überführt. Bei Einsatz von einem Überschuss des mindestens einen alkalischen Zusatzstoffes kann das entstandene Salz ausgefallen. Das Ausfällen des entstandenen Salzes wird erfindungsgemäß bevorzugt verhindert durch Einstellung des pH-Wertes. Bevorzugt ist der mindestens eine alkalische Zusatzstoff in einer Menge in einem Bereich von etwa 1 Gew.-% bis etwa 50 Gew.-%, besonders bevorzugt in einem Bereich von etwa 1,6 Gew.-% bis etwa 45 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, von dieser umfasst.According to the invention, the additive mixture comprises at least one alkaline additive. The at least one alkaline additive is preferably selected from a group comprising potassium hydroxide, sodium hydroxide, primary amines, secondary amines, tertiary amines, sodium carbonate, potassium carbonate or a mixture of these. One is preferred at least 10% to preferably 50% aqueous solution of the at least one alkaline additive, in particular of sodium hydroxide and potassium hydroxide, is used. For example, a 20% strength potassium hydroxide solution has 4.21 mol / l potassium hydroxide. For example, a 20% sodium hydroxide solution has 6.09 mol / l sodium hydroxide. The at least one alkaline additive reacts with the compounds generated by the at least one oxidizing agent in the bioethanol to be treated. If, for example, potassium hydroxide is used, the reaction with sulfuric acid formed from hydrogen sulfide produces potassium sulfate K 2 SO 4 . As a result of the reaction, which can preferably be carried out in two stages, the odor-forming compounds are converted into stable and soluble ions. If an excess of the at least one alkaline additive is used, the resulting salt can precipitate. According to the invention, the precipitation of the resulting salt is preferably prevented by adjusting the pH. The at least one alkaline additive is preferably in an amount in a range from about 1% by weight to about 50% by weight, particularly preferably in a range from about 1.6% by weight to about 45% by weight, based on the total amount of the additive mixture, comprised by this.
Bevorzugt umfasst die Additivmischung mindestens ein Triol. Weiter bevorzugt ist das mindestens eine Triol ausgewählt aus einer Gruppe umfassend Glycerin. Bevorzugt ist das mindestens eine Triol in einem Bereich von etwa 5 Gew.-% bis etwa 25 Gew.-%, weiter bevorzugt in einem Bereich von etwa 8 Gew.-% bis etwa 24 Gew.-% umfasst, bezogen auf die Gesamtmenge der Additivmischung.The additive mixture preferably comprises at least one triol. The at least one triol is more preferably selected from a group comprising glycerol. The at least one triol is preferably comprised in a range from about 5% by weight to about 25% by weight, more preferably in a range from about 8% by weight to about 24% by weight, based on the total amount of Additive mixture.
Bevorzugt umfasst die Additivmischung mindestens ein Vergällungsmittel. Weiter bevorzugt ist das mindestens eine Vergällungsmittel ausgewählt aus einer Gruppe umfassend Butanon, Phthalsäurediethylester, Thymol, Isopropanol, Tertiärbutanol, Denatoniumbenzoat, Methylethylketon, Methylisopropylketon, Ethylisoamylketon (5-Methyl-3-heptanon) und/oder Pyridinbasen. Da das mindestens eine Oxidationsmittel mit dem bereits dem Bioethanol beigefügten Vergällungsmittel reagieren kann, muss nach der Entfernung von Gerüchen durch die Additivmischung erneut mindestens ein Vergällungsmittel dem behandelten Bioethanol zugesetzt werden. Die erfindungsgemäß einsetzbaren Vergällungsmittel weisen bevorzugt einen ähnlichen Siedepunkt wie Ethanol auf, um eine Abtrennung desselben bei einer gegebenenfalls doch noch durchgeführten Destillation zu verhindern. Ein weiteres Auswahlkriterium des mindestens einen Vergällungsmittels ist ein intensiver unangenehmer Geschmack bei geringer Konzentration, um die Verwendung des Bioethanols ohne Besteuerung für alkoholische Getränke zu verhindern. Bevorzugt ist das mindestens eine Vergällungsmittel in einem Bereich von etwa 0,0005 Gew.-% bis etwa 30 Gew.-%, weiter bevorzugt in einem Bereich von etwa 0,001 Gew.-% bis etwa 25 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, von dieser umfasst.The additive mixture preferably comprises at least one denaturant. The at least one denaturant is more preferably selected from a group comprising butanone, diethyl phthalate, thymol, isopropanol, tertiary butanol, denatonium benzoate, methyl ethyl ketone, methyl isopropyl ketone, ethyl isoamyl ketone (5-methyl-3-heptanone) and / or pyridine bases. Since the at least one oxidizing agent can react with the denaturing agent already added to the bioethanol, at least one denaturing agent must be added again to the treated bioethanol after odors have been removed by the additive mixture. The denaturants which can be used according to the invention preferably have a boiling point similar to that of ethanol, in order to prevent separation of the same when a distillation may still be carried out. Another selection criterion of the at least one denaturing agent is an intense, unpleasant taste at a low concentration in order to prevent the use of bioethanol without taxation for alcoholic beverages. The at least one denaturant is preferably in a range from about 0.0005% by weight to about 30% by weight, more preferably in a range from about 0.001% by weight to about 25% by weight, based on the total amount the additive mixture, comprised of this.
Wird im Rahmen der Erfindung der Begriff "etwa" im Zusammenhang mit Werten oder Wertebereichen verwendet, so ist darunter ein Toleranzbereich zu verstehen, den der Fachmann auf diesem Gebiet für üblich erachtet, insbesondere ist ein Toleranzbereich von ±20 %, bevorzugt ±10 %, weiter bevorzugt ±5 %, noch weiter bevorzugt ±3 %, vorgesehen. Die in der vorliegenden Erfindung beanspruchten unteren Grenzwerte und die oberen Grenzwerte der verschiedenen Bereiche, insbesondere der Gewichtsprozentbereiche, aber nicht darauf beschränkt, können zur Definition neuer Bereiche miteinander kombiniert werden.If, within the scope of the invention, the term "approximately" is used in connection with values or value ranges, this is to be understood as a tolerance range which the person skilled in the art in this field considers normal, in particular a tolerance range of ± 20%, preferably ± 10%, more preferably ± 5%, even more preferably ± 3%, are provided. The lower limit values claimed in the present invention and the upper limit values of the various ranges, in particular the weight percentage ranges, but not limited thereto, can be combined with one another to define new ranges.
Soweit der Begriff Gewichtsprozent oder Gew.-% in Bezug auf die aus dem beanspruchten Verfahren und der beanspruchten Verwendung bestehenden Komponenten verwendet wird, bezieht sich der Begriff Gewichtsprozent auf die Menge einer oder mehrerer Komponenten im Verhältnis zur Gesamtmenge der verwendeten Komponenten, in der Regel der Additivmischung oder der erhaltenen Lösung im erfindungsgemäßen Verfahren, sofern nicht ausdrücklich etwas anderes angegeben ist. Der Ausdruck "Gew.-%" wird in der gesamten vorliegenden Erfindung als Abkürzung für Gewichtsprozent verwendet, soweit nicht anders angegeben.Insofar as the term percent by weight or% by weight is used in relation to the components consisting of the claimed method and the claimed use, the term percent by weight relates to the amount of one or more components in relation to the total amount of the components used, usually the Additive mixture or the solution obtained in the process according to the invention, unless expressly stated otherwise. The term "wt .-%" is used throughout the present invention as an abbreviation for percent by weight, unless otherwise specified.
Weiterhin betrifft die vorliegende Erfindung ein Verfahren zur Geruchsminderung in Bioethanol umfassend die Schritte:
- a) Verdünnen von Bioethanol durch mindestens ein Verdünnungsmittel;
- b) Hinzufügen von einer Additivmischung umfassend mindestens einen alkalischen Zusatzstoff und mindestens ein Oxidationsmittel;
- c) Homogenisieren der erhaltenen Lösung.
- a) dilution of bioethanol with at least one diluent;
- b) adding an additive mixture comprising at least one alkaline additive and at least one oxidizing agent;
- c) homogenizing the solution obtained.
Erfindungsgemäß wird Bioethanol mit einem Fehlgeruch behandelt. Das zu behandelnde Bioethanol liegt in einer Menge im Bereich von etwa 20 Gew.-% bis etwa 97 Gew.-%, noch weiter bevorzugt in einer Menge in einem Bereich von etwa 50 Gew.-% bis etwa 85 Gew.-%, bezogen auf die Gesamtmenge der erhaltenen Lösung, vor. Die erhaltene Lösung umfasst das zu behandelnde Bioethanol, das mindestens eine Verdünnungsmittel und die zuvor beschriebene, erfindungsgemäße Additivmischung.According to the invention, bioethanol is treated with an offensive odor. That to be treated Bioethanol is in an amount in the range from about 20% by weight to about 97% by weight, even more preferably in an amount in a range from about 50% by weight to about 85% by weight, based on the total amount the solution obtained. The solution obtained comprises the bioethanol to be treated, the at least one diluent and the above-described additive mixture according to the invention.
Erfindungsgemäß wird im Verfahrensschritt a) ein Verdünnungsmittel dem zu behandelnden Bioethanol zugesetzt. Bevorzugt ist das mindestens eine Verdünnungsmittel Wasser. Weiter bevorzugt ist das mindestens eine Verdünnungsmittel Leitungswasser oder deionisiertes Wasser. Deionisiertes Wasser ist Wasser ohne die im Quell- und Leitungswasser vorkommenden Salze, die als Anionen und Kationen gelöst sind, und wird in der Chemie und der Biologie als Lösungs- und manchmal auch als Reinigungsmittel verwendet. Der Verfahrensschritt a) Verdünnen des zu behandelnden Bioethanols wird bevorzugt vor dem Verfahrensschritt b) Hinzufügen einer Additivmischung durchgeführt. Bevorzugt ist das mindestens eine Verdünnungsmittel in einem Bereich von etwa 3 Gew.-% bis etwa 80 Gew.-% und weiter bevorzugt in einem Bereich von etwa 5 Gew-% bis etwa 50 Gew.-%, bezogen auf die Gesamtmenge der erhaltenen Lösung, von dieser umfasst.According to the invention, a diluent is added to the bioethanol to be treated in process step a). The at least one diluent is preferably water. The at least one diluent is more preferably tap water or deionized water. Deionized water is water without the salts found in spring and tap water, which are dissolved as anions and cations, and is used in chemistry and biology as a solvent and sometimes also as a cleaning agent. Process step a) diluting the bioethanol to be treated is preferably carried out before process step b) adding an additive mixture. The at least one diluent is preferably in a range from about 3% by weight to about 80% by weight and more preferably in a range from about 5% by weight to about 50% by weight, based on the total amount of the solution obtained , covered by this.
Bevorzugt liegt das Verhältnis zwischen der Menge an Wasser und der Menge an Bioethanol in einem Bereich von etwa 0,2 bis etwa 0,9, und noch weiter bevorzugt in einem Bereich von etwa 0,5 bis etwa 0,8. Das Verhältnis zwischen der Menge an Wasser und der Menge an Bioethanol ist auf die Verwendung der erhaltenen Lösung abgestimmt.The ratio between the amount of water and the amount of bioethanol is preferably in a range from about 0.2 to about 0.9, and even more preferably in a range from about 0.5 to about 0.8. The ratio between the amount of water and the amount of bioethanol is tailored to the use of the solution obtained.
Erfindungsgemäß wird im Verfahrensschritt b) die zuvor beschriebene, erfindungsgemäße Additivmischung dem zu behandelnden Bioethanol hinzugefügt. Das Hinzufügen der Additivmischung findet erfindungsgemäß sequenziell statt. Bei dem sequenziellen Hinzufügen der Additivmischung wird bevorzugt erst das mindestens eine Oxidationsmittel dem zu behandelnden Bioethanol zugesetzt, und dann der mindestens eine alkalische Zusatzstoff, alternativ kann die Zugabe des Oxidationsmittels und des alkalischen Zusatzstoffs in Abhängigkeit von den eingesetzten Verbindungen auch in umgekehrter Reihenfolge oder gleichzeitig erfolgen. Bevorzugt ist das mindestens eine Oxidationsmittel in einer Menge in einem Bereich von etwa 0,01 Gew.-% bis etwa 8 Gew.-%, besonders bevorzugt in einem Bereich von etwa 0,02 Gew.-% bis etwa 7 Gew.-%, bezogen auf die Gesamtmenge der erhaltenden Lösung, von dieser umfasst. In einer bevorzugten Ausführungsform wird nach dem Hinzufügen des mindestens einen Oxidationsmittels wird der mindestens eine alkalische Zusatzstoff hinzugefügt.According to the invention, the previously described additive mixture according to the invention is added to the bioethanol to be treated in process step b). According to the invention, the additive mixture is added sequentially. In the sequential addition of the additive mixture, the at least one oxidizing agent is preferably added to the bioethanol to be treated first, and then the at least one alkaline additive; alternatively, the oxidizing agent and the alkaline additive can also be added in reverse order or at the same time, depending on the compounds used . The at least one oxidizing agent is preferably in an amount in a range from about 0.01% by weight to about 8% by weight, particularly preferably in a range from about 0.02% by weight to about 7% by weight, based on the total amount of the solution obtained . In a preferred embodiment, after the addition of the at least one oxidizing agent, the at least one alkaline additive is added.
Bevorzugt wird mittels des alkalischen Zusatzstoffs ein pH-Wert der erhaltenen Lösung in einem Bereich von etwa 7 bis etwa 13 eingestellt. Zur Messung des pH-Wertes wird eine Probe der erhaltenen Lösung abgetrennt und soweit verdünnt, dass ein Wassergehalt von mindestens 50 Gew.-% erreicht ist. Dann wird der pH Wert mittels eines pH-Meter WTW 3310 mit der pH Elektrode SenTix 81 hergestellt von WTW bei einer Temperatur von 20°C gemessen. Bevorzugt ist der mindestens eine alkalische Zusatzstoff in einer Menge in einem Bereich von etwa 0,01 Gew.-% bis etwa 5 Gew.-%, besonders bevorzugt in einem Bereich von etwa 0,02 Gew.-% bis etwa 3 Gew.-%, bezogen auf die Gesamtmenge der erhaltenden Lösung, von dieser umfasst.The pH of the solution obtained is preferably set in a range from about 7 to about 13 by means of the alkaline additive. To measure the pH, a sample of the solution obtained is separated off and diluted to such an extent that a water content of at least 50% by weight is reached. The pH value is then measured using a WTW 3310 pH meter with the SenTix 81 pH electrode manufactured by WTW at a temperature of 20 ° C. The at least one alkaline additive is preferably in an amount in a range from about 0.01% by weight to about 5% by weight, particularly preferably in a range from about 0.02% by weight to about 3% by weight. %, based on the total amount of the solution obtained, comprised of this.
Das mindestens eine Vergällungsmittel wird bevorzugt nach dem mindestens einen Oxidationsmittel hinzugefügt. Bevorzugt wird das eine Vergällungsmittel nach Abbau eines möglichen Überschusses des mindestens einen Oxidationsmittels der erhaltenen Mischung hinzugefügt. Bevorzugt ist das mindestens eine Vergällungsmittel in einer Menge in einem Bereich von etwa 0,0001 Gew.-% bis etwa 5 Gew.-%, besonders bevorzugt in einem Bereich von etwa 0,0002 Gew.-% bis etwa 4 Gew.-%, bezogen auf die Gesamtmenge der erhaltenden Lösung, von dieser umfasst.The at least one denaturing agent is preferably added after the at least one oxidizing agent. The one denaturing agent is preferably added to the mixture obtained after a possible excess of the at least one oxidizing agent has been broken down. The at least one denaturant is preferably in an amount in a range from about 0.0001% by weight to about 5% by weight, particularly preferably in a range from about 0.0002% by weight to about 4% by weight , based on the total amount of the solution obtained, comprised by this.
Bevorzugt ist in einem weiteren Schritt die Zugabe von mindestens einem Triol umfasst. Bevorzugt ist das mindestens eine Triol in einer Menge in einem Bereich von etwa 0,01 Gew.-% bis etwa 5 Gew.-%, besonders bevorzugt in einem Bereich von etwa 0,1 Gew.-% bis etwa 4 Gew.-%, bezogen auf die Gesamtmenge der erhaltenden Lösung von dieser umfasst.The addition of at least one triol is preferably included in a further step. The at least one triol is preferably in an amount in a range from about 0.01% by weight to about 5% by weight, particularly preferably in a range from about 0.1% by weight to about 4% by weight , based on the total amount of the solution obtained from this.
Bevorzugt ist in einem weiteren Schritt die Zugabe von mindestens einem Reduktionsmittel. Weiter bevorzugt ist das mindestens eine Reduktionsmittel ausgewählt aus einer Gruppe umfassend Ascorbinsäure, Natriumascorbat, Sulfite, Thiosulfate Katalase oder eine Mischung dieser. Bevorzugt wird ein Überschuss des mindestens einen Oxidationsmittels durch das Hinzufügen von mindestens einem Reduktionsmittel neutralisiert. Durch das Neutralisieren des überschüssigen Oxidationsmittels wird die erhaltene Lösung, auch behandeltes Bioethanol genannt, lagerstabil. Das mindestens eine Reduktionsmittel wird tropfenweise zur erhaltenen Lösung hinzugegeben, bis kein überschüssiges Oxidationsmittel mehr vorhanden ist. Der Gehalt des mindestens einen Oxidationsmittels wird durch einen handelsüblichen Peroxid-Test, wie Peroxid-Teststäbchen MQuant® von Merck KGaA Deutschland bestimmt. Diese Gehaltsbestimmung wird während der Zugabe des mindestens einen Reduktionsmittels wiederholt bis der Peroxid-Test kein Oxidationsmittel mehr nachweist.In a further step, the addition of at least one reducing agent is preferred. The at least one reducing agent is more preferably selected from a group comprising ascorbic acid, sodium ascorbate, sulfites, thiosulfates, catalase or a mixture this. An excess of the at least one oxidizing agent is preferably neutralized by adding at least one reducing agent. By neutralizing the excess oxidizing agent, the solution obtained, also called treated bioethanol, is stable in storage. The at least one reducing agent is added dropwise to the resulting solution until there is no longer any excess oxidizing agent. The content of the at least one oxidizing agent is determined by a commercially available peroxide test, such as peroxide test sticks MQUANT ® from Merck KGaA Germany. This determination of the content is repeated during the addition of the at least one reducing agent until the peroxide test no longer detects any oxidizing agent.
Das sequenzielle Hinzufügen weist den Vorteil auf, eine Reaktion der einzelnen Komponenten der Additivmischung untereinander zu vermeiden. Bevorzugt ist die Additivmischung in einer Menge in einem Bereich von etwa 0,001 Gew.-% bis etwa 20 Gew.-%, weiter bevorzugt in einem Bereich von etwa 0,005 Gew.-% bis etwa 17,5 Gew.-%, bezogen auf die Gesamtmenge der erhaltenen Lösung, dieser hinzugefügt.The sequential addition has the advantage of preventing the individual components of the additive mixture from reacting with one another. The additive mixture is preferably in an amount in a range from about 0.001% by weight to about 20% by weight, more preferably in a range from about 0.005% by weight to about 17.5% by weight, based on the Total amount of the solution obtained, added to this.
Erfindungsgemäß wird die erhaltene Lösung im Verfahrensschritt c) homogenisiert. Das Homogenisieren kann bevorzugt während und nach den Verfahrensschritten a) und b) durchgeführt werden. Das erfindungsgemäße Homogenisieren umfasst beispielsweise ein Rühren und/oder Schütteln der erhaltenen Lösung.According to the invention, the solution obtained is homogenized in process step c). The homogenization can preferably be carried out during and after process steps a) and b). The homogenization according to the invention comprises, for example, stirring and / or shaking the solution obtained.
Bevorzugt werden sämtliche Verfahrensschritte bei Raumtemperatur durchgeführt. Raumtemperatur ist die durchschnittliche Raumlufttemperatur. Die Raumtemperatur liegt bevorzugt in einem Bereich von etwa 18 °C bis etwa 25 °C, weiter bevorzugt in einem Bereich von etwa 20 °C bis etwa 23 °C.All process steps are preferably carried out at room temperature. Room temperature is the average room air temperature. The room temperature is preferably in a range from about 18 ° C to about 25 ° C, more preferably in a range from about 20 ° C to about 23 ° C.
Die Geruchsbestimmung der erhaltenen Lösung im Sinne der vorliegenden Erfindung wird bevorzugt von mindestens zwei Personen durchgeführt werden, die unabhängig voneinander den Geruch bestimmen. Die Geruchsbestimmung wird in einem gut gelüfteten Raum durchgeführt. Die Proben werden in fest verschlossenen Gefäßen aufbewahrt, welche im geschlossenen Zustand geruchsfrei sein müssen. Die Proben werden bei Raumtemperatur beurteilt. Mit einer Pipette werden 3 bis 4 Tropfen auf eine 30°C erwärmte Oberfläche gegeben und zu einem dünnen Film verstrichen. Die Geruchsbeurteilung des verdunstenden Probenfilms wird durch leichtes Zufächeln des Geruchs olfaktorisch beurteilt. Nach jeder Probe wird das Gefäß wieder fest verschlossen. Als Vergleich wird dieser Vorgang unmittelbar vor der Probe oder nach der Probe einmal mit unbehandeltem Bioethanol und einmal mit reinem Ethanol durchgeführt. Diese Schritte können wiederholt werden. Es wurde ein Bewertungsschema für den Fehlgeruch des zu behandelnden Bioethanols erarbeitet. Das Bewertungsschema ist in Geruchskategorien mit Kennzahlen eingeteilt, wie in der folgenden Tabelle 1 dargestellt. Die zu beurteilende Probe wird von den Personen getrennt in eine der Geruchskategorien eingeteilt und die Abnahme des unangenehmen Geruchs mit der Kennzahl 10 bis zum vollständigen Verschwinden und einen Übergang zu einen neutralen Ethanolgeruch mit einer leicht fruchtigen Ester-Note bei der Kennzahl 1 quantifiziert.
Die Geruchsbestimmung wird zu mehreren Zeitpunkten durchgeführt. Bevorzugt wird die Geruchsbestimmung zum Zeitpunkt 0 Stunden, direkt nach der Zugabe von alkalischem Zusatzstoff und/oder Oxidationsmittel, und nach abgeschlossener Reaktion der Komponenten der erfindungsgemäßen Additivmischung mit dem zu behandelnden Bioethanol durchgeführt. Die Geruchsbestimmung wird nach Vollendung des Verfahrensschrittes c) des vorgenannten, erfindungsgemäßen Verfahrens durchgeführt, was dem Zeitpunkt 0 Stunden entspricht. Die Reaktion der Komponenten der Additivmischung ist regelmäßig nach spätestens 24 Stunden abgeschlossen. Eine finale Geruchsbestimmung wird daher bevorzugt 24 Stunden nach Beendigung des Verfahrensschrittes c) durchgeführt.The odor determination is carried out at several points in time. It is preferred to determine the odor at the time 0 hours, directly after the addition of the alkaline additive and / or oxidizing agent, and after the components have reacted the additive mixture according to the invention carried out with the bioethanol to be treated. The odor determination is carried out after the completion of method step c) of the aforementioned method according to the invention, which corresponds to the time 0 hours. The reaction of the components of the additive mixture is usually complete after 24 hours at the latest. A final odor determination is therefore preferably carried out 24 hours after the end of process step c).
Weiterhin betrifft die vorliegende Erfindung ein Produkt, hergestellt durch das vorgenannte, erfindungsgemäße Verfahren. Das erfindungsgemäße Produkt ist die erhaltene Lösung, welche in der vorliegenden Erfindung auch als geruchsfreier behandelter Bioethanol benannt ist. Der geruchsfreie behandelte Bioethanol wird bevorzugt als Basis für Reinigungs- und Desinfektionsmittel oder in der Kosmetikindustrie verwendet.The present invention further relates to a product produced by the aforementioned method according to the invention. The product according to the invention is the solution obtained, which in the present invention is also referred to as odorless treated bioethanol. The odor-free treated bioethanol is preferably used as a basis for cleaning agents and disinfectants or in the cosmetics industry.
Die mit der Erfindung erzielten Vorteile bestehen darin, dass kostengünstiger, geruchsintensiver Bioethanol schnell und kostengünstig behandelt werden kann, um dessen Fehlgeruch zu mindern, so dass dieser neuen Anwendungen zugeführt werden kann.The advantages achieved with the invention are that inexpensive, odor-intensive bioethanol can be treated quickly and inexpensively in order to reduce its off-odor, so that it can be used for new applications.
Eine beispielhafte erfindungsgemäße Verwendung einer Additivmischung umfasst bevorzugt mindestens einen alkalischen Zusatzstoff in einer Menge in einem Bereich von etwa 1 Gew.-% bis etwa 50 Gew.-% und mindestens ein Oxidationsmittel in einem Bereich von etwa 1 Gew.-% bis etwa 80 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, zur Minderung von Fehlgerüchen in Bioethanol.An exemplary use according to the invention of an additive mixture preferably comprises at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight .-%, based on the total amount of the additive mixture, to reduce bad odors in bioethanol.
Eine beispielhafte erfindungsgemäße Verwendung einer Additivmischung umfasst noch weiter bevorzugt mindestens einen alkalischen Zusatzstoff in einer Menge in einem Bereich von etwa 1 Gew.-% bis etwa 50 Gew.-% und mindestens ein Oxidationsmittel in einem Bereich von etwa 1 Gew.-% bis etwa 80 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, zur Minderung von Fehlgerüchen in Bioethanol, wobei das mindestens eine Oxidationsmittel ausgewählt ist aus einer Gruppe umfassend Wasserstoffperoxid, Ethanperoxosäure, Natriumpercarbonat, Harnstoffperoxohydrat oder einer Mischung dieser.An exemplary use according to the invention of an additive mixture comprises even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the total amount of the additive mixture, to reduce bad odors in bioethanol, the at least one oxidizing agent being selected from a group comprising hydrogen peroxide, ethane peroxy acid, sodium percarbonate, urea peroxohydrate or a mixture of these.
Eine beispielhafte erfindungsgemäße Verwendung einer Additivmischung umfasst noch weiter bevorzugt mindestens einen alkalischen Zusatzstoff in einer Menge in einem Bereich von etwa 1 Gew.-% bis etwa 50 Gew.-% und mindestens ein Oxidationsmittel in einem Bereich von etwa 1 Gew.-% bis etwa 80 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, zur Minderung von Fehlgerüchen in Bioethanol, wobei der mindestens eine alkalische Zusatzstoff ausgewählt ist aus einer Gruppe umfassend Kaliumhydroxid, Natriumhydroxid, primäre Amine, sekundäre Amine, tertiäre Amine, Natriumcarbonat, Kaliumcarbonat oder einer Mischung dieser.An exemplary use according to the invention of an additive mixture encompasses even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the Total amount of the additive mixture to reduce off-odors in bioethanol, the at least one alkaline additive being selected from a group comprising potassium hydroxide, sodium hydroxide, primary amines, secondary amines, tertiary amines, sodium carbonate, potassium carbonate or a mixture of these.
Eine beispielhafte erfindungsgemäße Verwendung einer Additivmischung umfasst noch weiter bevorzugt mindestens einen alkalischen Zusatzstoff in einer Menge in einem Bereich von etwa 1 Gew.-% bis etwa 50 Gew.-% und mindestens ein Oxidationsmittel in einem Bereich von etwa 1 Gew.-% bis etwa 80 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, zur Minderung von Fehlgerüchen in Bioethanol, wobei die Additivmischung mindestens ein Triol umfasst, wobei weiter bevorzugt das mindestens eine Triol ausgewählt ist aus einer Gruppe umfassend Glycerin und wobei das zumindest eine Triol bevorzugt in einem Bereich von etwa 5 Gew.-% bis etwa 25 Gew.-% umfasst ist, bezogen auf die Gesamtmenge der Additivmischung.An exemplary use according to the invention of an additive mixture comprises even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the total amount of the additive mixture, for reducing off-odors in bioethanol, the additive mixture comprising at least one triol, the at least one triol preferably being selected from a group comprising glycerol and the at least one triol preferably being in a range from about 5% by weight to about 25% by weight, based on the total amount of the additive mixture.
Eine beispielhafte erfindungsgemäße Verwendung einer Additivmischung umfasst noch weiter bevorzugt mindestens einen alkalischen Zusatzstoff in einer Menge in einem Bereich von etwa 1 Gew.-% bis etwa 50 Gew.-% und mindestens ein Oxidationsmittel in einem Bereich von etwa 1 Gew.-% bis etwa 80 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, zur Minderung von Fehlgerüchen in Bioethanol, wobei die Additivmischung weiter bevorzugt mindestens ein Vergällungsmittel umfasst, wobei das mindestens eine Vergällungsmittel ausgewählt ist aus einer Gruppe umfassend Butanon, Phthalsäurediethylester, Thymol, Isopropanol, Tertiärbutanol, Denatoniumbenzoat, Methylethylketon, Methylisopropylketon, Ethylisoamylketon (5-Methyl-3-heptanon) und/oder Pyridinbasen, und wobei das mindestens eine Vergällungsmittel bevorzugt in einem Bereich von etwa 0,0005 Gew.-% bis etwa 30 Gew.-% umfasst ist, bezogen auf die Gesamtmenge der Additivmischung.An exemplary use according to the invention of an additive mixture comprises even more preferably at least one alkaline additive in an amount in a range from about 1% by weight to about 50% by weight and at least one oxidizing agent in a range from about 1% by weight to about 80% by weight, based on the total amount of the additive mixture, for reducing off-odors in bioethanol, the additive mixture further preferably comprising at least one denaturing agent, the at least one denaturing agent being selected from a group comprising butanone, diethyl phthalate, thymol, isopropanol, and tertiary butanol , Denatonium benzoate, methyl ethyl ketone, methyl isopropyl ketone, ethyl isoamyl ketone (5-methyl-3-heptanone) and / or pyridine bases, and wherein the at least one denaturant is preferably comprised in a range from about 0.0005% by weight to about 30% by weight , based on the total amount of the additive mixture.
Eine beispielhafte erfindungsgemäße Verwendung einer Additivmischung umfasst bevorzugt mindestens einen alkalischen Zusatzstoff in einer Menge in einem Bereich von etwa 1 Gew.-% bis etwa 45 Gew.-% und mindestens ein Oxidationsmittel in einem Bereich von etwa 1 Gew.-% bis etwa 75 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, zur Minderung von Fehlgerüchen in Bioethanol.An exemplary use according to the invention of an additive mixture preferably comprises at least one alkaline additive in an amount in a range of about 1% by weight up to about 45% by weight and at least one oxidizing agent in a range from about 1% by weight to about 75% by weight, based on the total amount of the additive mixture, to reduce bad odors in bioethanol.
Eine beispielhafte erfindungsgemäße Verwendung einer Additivmischung umfasst bevorzugt mindestens einen alkalischen Zusatzstoff in einer Menge in einem Bereich von etwa 1,6 Gew.-% bis etwa 45 Gew.-% und mindestens ein Oxidationsmittel in einem Bereich von etwa 1,6 Gew.-% bis etwa 75 Gew.-%, bezogen auf die Gesamtmenge der Additivmischung, zur Minderung von Fehlgerüchen in Bioethanol.An exemplary use according to the invention of an additive mixture preferably comprises at least one alkaline additive in an amount in a range from about 1.6% by weight to about 45% by weight and at least one oxidizing agent in a range from about 1.6% by weight up to about 75% by weight, based on the total amount of the additive mixture, to reduce off-smells in bioethanol.
Ein beispielhaftes erfindungsgemäßes Verfahren zur Geruchsminderung in Bioethanol bevorzugt umfassend die Schritte:
- a) Verdünnen von etwa 20 Gew.-% bis etwa 97 Gew.-% Bioethanol durch etwa 3 Gew.-% bis etwa 80 Gew.-% mindestens eines Verdünnungsmittels;
- b) Hinzufügen von etwa 0,001 Gew.- % bis etwa 20 Gew.-% einer Additivmischung umfassend etwa 0,01 Gew.-% bis etwa 50 Gew.-% mindestens eines alkalischen Zusatzstoffes und etwa 0,01 Gew.-% bis etwa 80 Gew.-% mindestens eines Oxidationsmittels, wobei die Gew-%-Angaben des mindestens einen alkalischen Zusatzstoffes und des mindestens einen Oxidationsmittels bezogen sind auf die Gesamtmenge der Additivmischung;
- c) Homogenisieren der erhaltenen Lösung,
- a) diluting from about 20% by weight to about 97% by weight of bioethanol with about 3% by weight to about 80% by weight of at least one diluent;
- b) adding about 0.001% by weight to about 20% by weight of an additive mixture comprising about 0.01% by weight to about 50% by weight of at least one alkaline additive and about 0.01% by weight to about 80% by weight of at least one oxidizing agent, the weight percentages of the at least one alkaline additive and of the at least one oxidizing agent being based on the total amount of the additive mixture;
- c) homogenizing the solution obtained,
Ein beispielhaftes erfindungsgemäßes Verfahren zur Geruchsminderung in Bioethanol bevorzugt umfassend die Schritte:
- a) Verdünnen von etwa 20 Gew.-% bis etwa 97 Gew.-% Bioethanol durch etwa 3 Gew.-% bis etwa 80 Gew.-% mindestens eines Verdünnungsmittels;
- b) Hinzufügen von etwa 0,001 Gew.- % bis etwa 20 Gew.-% einer Additivmischung umfassend etwa 0,01 Gew.-% bis etwa 50 Gew.-% mindestens eines alkalischen Zusatzstoffes und etwa 0,01 Gew.-% bis etwa 80 Gew.-% mindestens eines Oxidationsmittels, wobei die Gew-%- Angaben des mindestens einen alkalischen Zusatzstoffes und des mindestens einen Oxidationsmittels bezogen sind auf die Gesamtmenge der Additivmischung;
- c) Homogenisieren der erhaltenen Lösung,
- a) diluting from about 20% by weight to about 97% by weight of bioethanol with about 3% by weight to about 80% by weight of at least one diluent;
- b) adding about 0.001% by weight to about 20% by weight of an additive mixture comprising about 0.01% by weight to about 50% by weight of at least one alkaline additive and about 0.01% by weight to about 80% by weight of at least one oxidizing agent, the% by weight of the at least one alkaline additive and the at least one oxidizing agent are based on the total amount of the additive mixture;
- c) homogenizing the solution obtained,
Ein beispielhaftes erfindungsgemäßes Verfahren zur Geruchsminderung in Bioethanol bevorzugt umfassend die Schritte:
- a) Verdünnen von etwa 20 Gew.-% bis etwa 97 Gew.-% Bioethanol durch etwa 3 Gew.-% bis etwa 80 Gew.-% mindestens eines Verdünnungsmittels;
- b) Hinzufügen von etwa 0,001 Gew.- % bis etwa 20 Gew.-% einer Additivmischung umfassend etwa 0,01 Gew.-% bis etwa 50 Gew.-% mindestens eines alkalischen Zusatzstoffes und etwa 0,01 Gew.-% bis etwa 80 Gew.-% mindestens eines Oxidationsmittels, wobei die Gew-%- Angaben des mindestens einen alkalischen Zusatzstoffes und des mindestens einen Oxidationsmittels bezogen sind auf die Gesamtmenge der Additivmischung;
- c) Homogenisieren der erhaltenen Lösung,
- a) diluting from about 20% by weight to about 97% by weight of bioethanol with about 3% by weight to about 80% by weight of at least one diluent;
- b) adding about 0.001% by weight to about 20% by weight of an additive mixture comprising about 0.01% by weight to about 50% by weight of at least one alkaline additive and about 0.01% by weight to about 80% by weight of at least one oxidizing agent, the weight percentages of the at least one alkaline additive and of the at least one oxidizing agent being based on the total amount of the additive mixture;
- c) homogenizing the solution obtained,
Ein beispielhaftes erfindungsgemäßes Verfahren zur Geruchsminderung in Bioethanol bevorzugt umfassend die Schritte:
- a) Verdünnen von etwa 20 Gew.-% bis etwa 97 Gew.-% Bioethanol durch etwa 3 Gew.-% bis etwa 80 Gew.-% mindestens eines Verdünnungsmittels;
- b) Hinzufügen von etwa 0,001 Gew.- % bis etwa 20 Gew.-% einer Additivmischung umfassend etwa 0,01 Gew.-% bis etwa 50 Gew.-% mindestens eines alkalischen Zusatzstoffes und etwa 0,01 Gew.-% bis etwa 80 Gew.-% mindestens eines Oxidationsmittels, wobei die Gew-%- Angaben des mindestens einen alkalischen Zusatzstoffes und des mindestens einen Oxidationsmittels bezogen sind auf die Gesamtmenge der Additivmischung;
- c) Homogenisieren der erhaltenen Lösung,
- a) diluting from about 20% by weight to about 97% by weight of bioethanol with about 3% by weight to about 80% by weight of at least one diluent;
- b) adding about 0.001% by weight to about 20% by weight of an additive mixture comprising about 0.01% by weight to about 50% by weight of at least one alkaline additive and about 0.01% by weight to about 80% by weight of at least one oxidizing agent, the weight percentages of the at least one alkaline additive and of the at least one oxidizing agent being based on the total amount of the additive mixture;
- c) homogenizing the solution obtained,
Ein beispielhaftes erfindungsgemäßes Verfahren zur Geruchsminderung in Bioethanol bevorzugt umfassend die Schritte:
- a) Verdünnen von etwa 20 Gew.-% bis etwa 97 Gew.-% Bioethanol durch etwa 3 Gew.-% bis etwa 80 Gew.-% mindestens eines Verdünnungsmittels;
- b) Hinzufügen von etwa 0,001 Gew.- % bis etwa 20 Gew.-% einer Additivmischung umfassend etwa 0,01 Gew.-% bis etwa 50 Gew.-% mindestens eines alkalischen Zusatzstoffes und etwa 0,01 Gew.-% bis etwa 80 Gew.-% mindestens eines Oxidationsmittels, wobei die Gew-%- Angaben des mindestens einen alkalischen Zusatzstoffes und des mindestens einen Oxidationsmittels bezogen sind auf die Gesamtmenge der Additivmischung;
- c) Homogenisieren der erhaltenen Lösung,
- a) diluting from about 20% by weight to about 97% by weight of bioethanol with about 3% by weight to about 80% by weight of at least one diluent;
- b) adding about 0.001% by weight to about 20% by weight of an additive mixture comprising about 0.01% by weight to about 50% by weight of at least one alkaline additive and about 0.01% by weight to about 80% by weight of at least one oxidizing agent, the weight percentages of the at least one alkaline additive and of the at least one oxidizing agent being based on the total amount of the additive mixture;
- c) homogenizing the solution obtained,
Ein beispielhaftes erfindungsgemäßes Verfahren zur Geruchsminderung in Bioethanol bevorzugt umfassend die Schritte:
- a) Verdünnen von etwa 20 Gew.-% bis etwa 97 Gew.-% Bioethanol durch etwa 3 Gew.-% bis etwa 80 Gew.-% mindestens eines Verdünnungsmittels;
- b) Hinzufügen von etwa 0,001 Gew.- % bis etwa 20 Gew.-% einer Additivmischung umfassend etwa 0,01 Gew.-% bis etwa 50 Gew.-% mindestens eines alkalischen Zusatzstoffes und etwa 0,01 Gew.-% bis etwa 80 Gew.-% mindestens eines Oxidationsmittels, wobei die Gew-%- Angaben des mindestens einen alkalischen Zusatzstoffes und des mindestens einen Oxidationsmittels bezogen sind auf die Gesamtmenge der Additivmischung;
- c) Homogenisieren der erhaltenen Lösung,
- a) diluting from about 20% by weight to about 97% by weight of bioethanol with about 3% by weight to about 80% by weight of at least one diluent;
- b) adding about 0.001% by weight to about 20% by weight of an additive mixture comprising about 0.01% by weight to about 50% by weight of at least one alkaline additive and about 0.01% by weight to about 80% by weight of at least one oxidizing agent, the% by weight data of the at least one alkaline additive and of the at least one oxidizing agent being based on the total amount of the additive mixture;
- c) homogenizing the solution obtained,
In den vorstehenden bevorzugten Ausführungsformen der erfindungsgemäßen Verwendung einer Additivmischung, des erfindungsgemäßen Verfahrens und des durch das erfindungsgemäße Verfahren hergestellten Produktes handelt es sich um nicht einschränkende bevorzugte Beispiele. Auch eine Kombination der genannten Bereiche und Komponenten eines jeden Beispiels mit einem anderen oder mehreren anderen Beispielen untereinander ist möglich. Die vorliegende Erfindung wird im Folgenden anhand der nicht einschränkenden Ausführungsbeispiele näher beschrieben.The above preferred embodiments of the use according to the invention of an additive mixture, the method according to the invention and the product produced by the method according to the invention are non-limiting preferred examples. A combination of the named areas and components of each example with one or more other examples is also possible. The present invention is described in more detail below with reference to the non-limiting exemplary embodiments.
Die pH-Wert Messung wurde mittels zweier Methoden durchgeführt. um den pH-Wert zu verifizieren:
- Methode 1: Die Probe wurde 1:1 in deionisiertem Wasser verdünnt. Anschließend wurde der pH-Wert gemessen mittels eines pH-Meters WTW 3310 mit einer pH Elektrode SenTix 81, hergestellt von WTW Xylem Analytics Germany Sales GmbH & Co. KG Deutschland, für einen Messbereich von 0 pH bis 14 pH und verwendbar in einem Temperaturbereich von 0°C bis 100°C, wobei die pH-Wert Messung bei 20°C durchgeführt wurde. Das pH-Meter wurde mittels der Pufferlösungen WTW-Pufferlösung pH 9.180, WTW-Pufferlösung pH 6.865, WTW-Pufferlösung pH 4.006 und WTW-Pufferlösung pH 1.679 durch Titration mit einer 3 mol/l Kaliumchlorid-Lösung kalibriert.
- Methode 2: Bei einer unverdünnten Probe wurde der pH-Wert zusätzlich mittels pH-Indikatorstäbchen gemessen, wobei das pH-Indikatorstäbchen ein nicht blutender Universal Indikator für den pH-Wert Bereich von pH 0 bis pH 14 vorgesehen ist und von Merck KGaA stammt. Die pH-Wert Messung wurde bei Raumtemperatur durchgeführt.
- Method 1: The sample was diluted 1: 1 in deionized water. The pH was then measured using a WTW 3310 pH meter with a SenTix 81 pH electrode, manufactured by WTW Xylem Analytics Germany Sales GmbH & Co. KG Germany, for a measuring range from 0 pH to 14 pH and usable in a temperature range of 0 ° C to 100 ° C, with the pH value measurement being carried out at 20 ° C. The pH meter was measured using the buffer solutions WTW buffer solution pH 9.180, WTW buffer solution pH 6.865, WTW buffer solution pH 4.006 and WTW buffer solution pH 1.679 by titration with a 3 mol / l potassium chloride solution calibrated.
- Method 2: The pH value of an undiluted sample was also measured using a pH indicator stick, the pH indicator stick being a non-bleeding universal indicator for the pH value range from pH 0 to pH 14 and coming from Merck KGaA. The pH value measurement was carried out at room temperature.
Mit beiden pH-Wert Messungen wurden gleiche Werte ermittelt.The same values were determined with both pH measurements.
Die folgenden Verbindungen wurden bei den erfindungsgemäßen Ausführungsbeispielen A1 bis A7 und dem Vergleichsbeispiel A8 der Tabelle 2 verwendet.The following compounds were used in working examples A1 to A7 according to the invention and comparative example A8 in Table 2.
Es wurde Bioethanol mit einer Reinheit von 98,7 Vol% verwendet. Deionisiertes Wasser wurde als Verdünnungsmittel eingesetzt. Es wurde weiterhin Glycerin mit einer Reinheit von 86,5% verwendet. Wässrige Natronlauge als alkalischer Zusatzstoff wurde in einer Konzentration von 6,09 mol/l, was einer 20%igen Lösung entspricht verwendet. Wässrige Kalilauge als alkalischer Zusatzstoff wurde mit einer Konzentration von 4,21 mol/l, was einer 20%igen Lösung entspricht, verwendet. Als Oxidationsmittel wurde eine Wasserstoffperoxid-Lösung mit einer Konzentration von 9,80 mol/l, was einer 30 %igen Lösung entspricht, und mit einem pH-Wert von ≤ 3,5 pH bei 20°C und einer Dichte von 1,11 g/ml bei 20°C verwendet. Als Oxidationsmittel wurde weißes, pulverförmiges Natriumpercarbonat mit einer Reinheit von 99 % verwendet. Ethanolamin als alkalischer Zusatzstoff wurde mit einer Dichte von 1,02 g/ml, einer kinematischen Viskosität von 20 mm2/s bei 23°C und einer Reinheit von 99 % verwendet. Aus den vorgenannten Komponenten wurden Lösungen gemäß der folgenden Tabelle 2 und der nachstehenden Versuchsbeschreibung hergestellt.Bioethanol with a purity of 98.7% by volume was used. Deionized water was used as a diluent. Glycerin with a purity of 86.5% was also used. Aqueous sodium hydroxide solution was used as an alkaline additive in a concentration of 6.09 mol / l, which corresponds to a 20% solution. Aqueous potassium hydroxide solution was used as an alkaline additive with a concentration of 4.21 mol / l, which corresponds to a 20% solution. A hydrogen peroxide solution with a concentration of 9.80 mol / l, which corresponds to a 30% solution, and with a pH value of 3.5 pH at 20 ° C. and a density of 1.11 g was used as the oxidizing agent / ml used at 20 ° C. White, powdery sodium percarbonate with a purity of 99% was used as the oxidizing agent. Ethanolamine as an alkaline additive was used with a density of 1.02 g / ml, a kinematic viscosity of 20 mm 2 / s at 23 ° C. and a purity of 99%. Solutions according to Table 2 below and the description of the experiment below were prepared from the aforementioned components.
Bioethanol wurde in einem verschließbaren Reaktionsgefäß bei Raumtemperatur vorgelegt. Deionisiertes Wasser wurde dem vorgelegten Bioethanol zugegeben. Nachdem die Bioethanol-Wasser Lösung homogenisiert wurde, wurde Wasserstoffperoxid hinzugefügt. Nach vollständiger Zugabe von Wasserstoffperoxid wurden der alkalische Zusatzstoff und gegebenenfalls weitere Komponenten, wie Glycerin, hinzugegeben. Die erhaltene Lösung wurde durch Rühren homogenisiert. Die erste Geruchsbestimmung gemäß der vorgenannten Methode und eine pH-Wert Messung durch ein pH-Meter WTW 3310 mit der pH Elektrode SenTix 81 bei 20°C wurde zum Zeitpunkt 0 Stunden durchgeführt. Nach 24 Stunden wurde eine zweite Geruchsbestimmung und pH-Wert Messung vorgenommen.Bioethanol was placed in a sealable reaction vessel at room temperature. Deionized water was added to the submitted bioethanol. After the bioethanol-water solution was homogenized, hydrogen peroxide was added. After all of the hydrogen peroxide had been added, the alkaline additive and, if necessary, further components, such as glycerine, were added. The resulting solution was homogenized by stirring. The first odor determination according to the aforementioned method and a pH value measurement by a pH meter WTW 3310 with the pH electrode SenTix 81 at 20 ° C was carried out at the time 0 hours. After 24 hours, a second odor determination and pH value measurement were carried out.
Zusammensetzung der Lösungen der erfindungsgemäßen Ausführungsbeispiele A1 bis A7 und einem Vergleichsbeispiel A8 werden in der folgenden Tabelle 2 dargestellt, wobei die Mengen in Gew.%, bezogen auf die Gesamtmenge der Zusammensetzung, angegeben sind.
Die Geruchsbestimmung der erfindungsgemäßen Ausführungsbeispiele A1 bis A7 und des Vergleichsbeispiel A8 wurde nach Durchführen des oben angegebenen Verfahrens zum Zeitpunkt 0 h und eine weitere Geruchsbestimmung nach 24 h durchgeführt. Die experimentellen Ergebnisse der Geruchsbestimmung der erfindungsgemäßen Ausführungsbeispiele A1 bis A7 und dem Vergleichsbeispiel A8 sind in der nachstehenden Tabelle 3 aufgeführt.
Das Ausführungsbeispiel A1 mit 20%iger Kalilauge und 30%igem Wasserstoffperoxid weist eine vollständige Geruchsminderung nach 24 h auf. Die Ausführungsbeispiele A2 und A3 mit Kalilauge, Glycerin und Wasserstoffperoxid weisen wie A1 eine vollständige Geruchsminderung bei einem Wasserstoffperoxid-Gehalt von 0,1 Gew.-% und 4,63 Gew.-% auf. Somit kann der Fehlgeruch durch eine Zugabe von Wasserstoffperoxid in einem Bereich von 0,1 Gew.-% bis 5 Gew.-%, der verwendeten 30% igen Wasserstoffperoxid-Lösung, vollständig gemindert werden. Der Fehlgeruch des Ausführungsbeispiels A4 ist nach 24 h bis zu der Geruchskennzahl 1 reduziert. Ein niedriger Wasserstoffperoxidgehalt und ein niedriger Kalilaugen-Gehalt gemäß A4 weisen eine gleichbleibende Geruchsminderung auf auch bei einem etwas niedrigerem pH-Wert. A5 weist keinen Fehlgeruch nach 24 h auf, was dafür spricht, das Natronlauge alternativ zu Kalilauge einsetzbar ist. Das Ausführungsbeispiel A6 mit Ethanolamin als alkalischem Zusatzstoff zeigte nach 24 h noch einen leichten Fehlgeruch "leicht sauer nach Essig" entsprechend der Geruchskennzahl 3 auf. Offensichtlich ist Ethanolamin als alkalischer Zusatzstoff Kalilauge und Natronlauge bei gleichem Wasserstoffperoxidgehalt in seiner Wirkung etwas unterlegen, liefert aber gleichwohl gute Ergebnisse. Das Ausführungsbeispiel A7 mit Natriumpercarbonat als Oxidationsmittel weist vergleichbare Ergebnisse, wie das Ausführungsbeispiel A3 mit Wasserstoffperoxid. Das Vergleichsbeispiel A8 mit einer Geruchskennzahl von 6 nach 24 h weist keine vollständige Minderung des Fehlgeruches auf. Der pH-Wert des Vergleichsbeispiels A8 liegt bei 3 pH, was die unzureichende Minderung des Fehlgeruchs des Bioethanols begründen dürfte als auch das Fehlen des alkalischen Zusatzstoffes.The embodiment example A1 with 20% potassium hydroxide solution and 30% hydrogen peroxide shows a complete odor reduction after 24 hours. The exemplary embodiments A2 and A3 with potassium hydroxide solution, glycerine and hydrogen peroxide, like A1, have a complete odor reduction with a hydrogen peroxide content of 0.1% by weight and 4.63% by weight. The off-odor can thus be completely reduced by adding hydrogen peroxide in a range from 0.1% by weight to 5% by weight of the 30% strength hydrogen peroxide solution used. The off-odor in exemplary embodiment A4 is reduced to 1 after 24 hours. A low hydrogen peroxide content and a low potassium hydroxide content according to A4 indicate a constant reduction in odor, even at a slightly lower pH value. A5 has no off-odor after 24 hours, which suggests that caustic soda can be used as an alternative to caustic potash. Exemplary embodiment A6 with ethanolamine as the alkaline additive still had a slight off-odor "slightly acidic like vinegar" corresponding to the odor index 3 after 24 hours. Obviously, ethanolamine, as an alkaline additive, is somewhat inferior to potassium hydroxide and sodium hydroxide solution with the same hydrogen peroxide content, but nevertheless delivers good results. The exemplary embodiment A7 with sodium percarbonate as the oxidizing agent shows comparable results to the exemplary embodiment A3 with hydrogen peroxide. Comparative example A8 with an odor index of 6 after 24 hours does not show a complete reduction in the off-odor. The pH of Comparative Example A8 is 3 pH, which is likely to explain the insufficient reduction in the off-odor of the bioethanol and the lack of the alkaline additive.
Die Beispiele der erfindungsgemäßen Verwendung einer Additivzusammensetzung im erfindungsgemäßen Verfahren umfassend insbesondere Natronlauge und/oder Kalilauge als alkalischer Zusatzstoff und Wasserstoffperoxid als Oxidationsmittel zeigen deutlich, dass insbesondere diese Kombinationen einen Fehlgeruch von Bioethanol vollständig mindern können und damit eine kostengünstige, einfache Möglichkeit zur Verfügung stellen, Bioethanol auch anderen gewerblichen Nutzungsmöglichkeiten zuzuführen, insbesondere im Bereich der Desinfektionsmittel und der Kosmetik.The examples of the use according to the invention of an additive composition in the process according to the invention comprising in particular sodium hydroxide solution and / or potassium hydroxide solution as an alkaline additive and hydrogen peroxide as an oxidizing agent clearly show that these combinations in particular can completely reduce an off-smell of bioethanol and thus provide an inexpensive, simple option, bioethanol can also be used for other commercial purposes, especially in the field of disinfectants and cosmetics.
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