US20080313956A1 - Process for increasing the storage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel - Google Patents
Process for increasing the storage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel Download PDFInfo
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- US20080313956A1 US20080313956A1 US12/157,692 US15769208A US2008313956A1 US 20080313956 A1 US20080313956 A1 US 20080313956A1 US 15769208 A US15769208 A US 15769208A US 2008313956 A1 US2008313956 A1 US 2008313956A1
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- biodiesel
- bht
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 77
- 238000003860 storage Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- ZRDUANIDHBCCAO-UHFFFAOYSA-N (2,4-ditert-butylphenyl)methanol Chemical compound CC(C)(C)C1=CC=C(CO)C(C(C)(C)C)=C1 ZRDUANIDHBCCAO-UHFFFAOYSA-N 0.000 title description 3
- 239000011550 stock solution Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 10
- 235000015073 liquid stocks Nutrition 0.000 claims abstract description 5
- RJKPEKIHHFNMGS-UHFFFAOYSA-N 2,4-ditert-butyl-3-methylphenol Chemical compound CC1=C(C(C)(C)C)C=CC(O)=C1C(C)(C)C RJKPEKIHHFNMGS-UHFFFAOYSA-N 0.000 claims abstract 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- 239000008162 cooking oil Substances 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 235000019737 Animal fat Nutrition 0.000 claims 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 45
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 45
- 229920000642 polymer Polymers 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 unsaturated fatty acid methyl esters Chemical class 0.000 description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001382 dynamic differential scanning calorimetry Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- 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
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
- C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
-
- 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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- the invention relates to a process for increasing the storage stability of biodiesel and more specifically, the invention relates to the use of 2,4-di-tert-butylhydroxytoluene (referred to hereinbelow as BHT) for increasing the storage stability of biodiesel.
- BHT 2,4-di-tert-butylhydroxytoluene
- Biodiesel which is currently being used to an increasing extent to replace petroleum diesel as a fuel for diesel engines, for combined heating and power stations, ships and boats, as well as motor vehicles.
- Biodiesel comprising of fatty acid alkyl esters, which are predominantly fatty acid methyl esters, is obtained by transesterification, in which vegetable oils such as rapeseed oil, soya oil, palm oils and other vegetable oils used in cooking oil or animal fats, are reacted with methanol in the presence of a catalyst (usually sodium hydroxide solution). Also obtained in addition to the fatty acid methyl esters which can be used as biodiesel is glycerol.
- biodesel is disadvantaged by its low storage stability. This is caused by the decomposition of the biodesel's high content of unsaturated fatty esters into short chain products, which reduces the energy value of this alternative fuel.
- the decomposition leads to precipitation, which is recognizable as cloudiness of the biodiesel.
- the resulting decomposition products are peroxides, aldehydes and short-chain free fatty acids which form soluble and insoluble polymers as precipitates.
- the acids tend to corrode injection systems, pumps and nozzles of diesel engines.
- the insoluble polymers when crosslinked, can block the nozzles and lead to sparingly soluble deposits. This considerably restricts the functioning of the diesel engines.
- biodiesel In addition, soluble and insoluble polymers which are formed by oxidative degradation from the overall decomposition products cause incomplete combustion with soot formation, which can in some cases lead to engine damage. Therefore, none of these decomposition products should be present in the biodiesel. Nonetheless, the increased use of biodiesel as an alternative fuel derived from renewable raw materials makes it absolutely necessary to increase the storage stability of biodiesel.
- BHT 2,4-di-tert-butylhydroxytoluene
- 2,6-di-tert-butyl-p-cresol 2,6-di-tert-butyl-p-cresol
- the present invention therefore provides a process for increasing the storage stability of biodiesel, in which a liquid stock solution, based on the stock solution, comprises 15 to 60% by weight of BHT dissolved in biodiesel is metered into the biodiesel to be stabilized up to a concentration of 0.005 to 2% by weight of BHT, based on the overall solution of biodiesel.
- FIG. 1 is a graphical representation of the results of Rancimate test showing addition of increasing amounts of BHT and the percent content of C18 acid methyl ester in the biodiesel correlating to the ppm of BHT added.
- FIG. 2 shows that the difference in cloudiness before (left side) and after addition of BHT (right side).
- biodiesel refers to all saturated and unsaturated fatty acid alkyl esters, in particular fatty acid methyl esters, which can be used as biodiesel fuel, as customarily available under the name biodiesel as a fuel in automobiles for diesel engines in motor vehicles, combined heating and power plants, ships and boats, and other stationary diesel engines.
- the fatty acid methyl esters used as biodiesel are C 14 -C 24 fatty acid methyl esters which may be pure or in a mixture.
- the biodiesels used in the process according to the invention may additionally comprise all customary additives as used, for example, to increase the winter stability of biodiesel.
- the biodiesels having storage stability improved by the process according to the invention are prepared by transesterification of methanol with vegetable oils such as rapeseed oil, soya oil, palm oil, used cooking oils and fats or animal fats.
- the biodiesel which is stabilized in accordance with the invention is preferably that which has been obtained from rapeseed oil or soya oil by the transesterification mentioned above.
- “storage stability” means reduced cloudiness of the biodiesel, said cloudiness resulting from the reaction of decomposition products formed by oxidative processes in the biodiesel, giving rise to soluble and insoluble polymers which manifest in the form of precipitation.
- the invention further provides a process for preparing a liquid stock solution for use in increasing the storage stability of biodiesel, in which liquefied, optionally distilled, BHT is metered at a temperature in the range from 70 to 120° C., preferably 90 to 120° C., with stirring into biodiesel up to a concentration of 15 to 60% by weight of BHT, based on the stock solution.
- BHT is a solid at room temperature and can only be metered into the biodiesel at room temperature with great difficulty.
- the inventive stock solution comprising 15 to 60% by weight of BHT, preferably 20 to 40% by weight of BHT, is a highly concentrated solution of BHT in biodiesel which is liquid and meterable and can be very easily metered into the biodiesel to be stabilized. Even after a prolonged period, surprisingly, no precipitation of BHT out of this highly concentrated stock solution can be detected.
- the stock solution mentioned can be metered into the biodiesel to be stabilized up to a concentration of 0.005% by weight to 2% by weight, preferably 0.1 to 1% by weight, based on the overall solution of biodiesel. It is also possible to add higher concentrations of BHT to the biodiesel. The greatest stability effects are observed up to a concentration of 2% by weight.
- the inventively stabilized biodiesel has considerably improved storage stability, i.e., no undesired precipitation of insoluble polymers generated by oxidative degradation is detected in the inventively stabilized biodiesel.
- BHT advantageously leads to an increase in the solidification point of the biodiesel.
- solidification point refers to the temperature at which the biodiesel begins to crystallize out.
- the invention further provides the use of BHT for increasing the storage stability of biodiesel by preventing the cloudiness of biodiesel as a result of the decomposition products formed by oxidation processes.
- the cloudiness manifests itself in the form of precipitation.
- this precipitation can now be prevented from blocking engine nozzles or generating undesired deposits in the internal engine chamber (pistons, lines) by incomplete combustion, which can lead to engine damage.
- the invention further provides the storage-stabilized biodiesel itself which contains 0.005 to 2% by weight of dissolved BHT.
- Biodiesel (from rapeseed oil) was subjected to a Rancimate test admixed with increasing amounts of BHT (trade product from Bayer AG: Baynox®).
- the Rancimate 679 (Metrohm) consists of a control section and a wet section. In the wet section, the samples are heated and blown through by air in the presence of copper. During the oxidative ageing, short-chain, volatile organic acids are formed and are introduced into a measuring cell filled with distilled water. The conductivity is measured and recorded there continuously.
- the end of the ageing and oxidative stability is indicated by a steep increase in the conductivity.
- the time until the turning point is reached is referred to as the induction period and serves as a measure for the ageing stability.
- Time 120 minutes at 70° C. while passing through 60 ml/h of air/hour.
- FIG. 1 shows the results in graphical form.
- BHT is able to limit the degradation of unsaturated fatty acid methyl esters in the biodiesel as a function of dose.
- a 5 l flask having a narrow neck was charged with 2 l of biodiesel, and a second flask with the same amount, but admixed with 0.05% of BHT.
- the vessels were not sealed and left to stand at room temperature with occasional shaking (2-3 times per week). After approximately 6 weeks, the first cloudiness could be observed in the product which had not been admixed with BHT. After a further week, cloudiness as a result of insoluble polymers could be clearly seen.
- Biodiesel was investigated using oxygen under pressure (10 bar) by the DSC method (Differential Scanning Calorimetry according to DIN No. 51007). To this end, pure biodiesel and biodiesel with increasing amounts of BHT were used in the test arrangement.
- Determination of the heat flow to a sample, measured relative to a reference sample, both of which are subjected to a defined temperature program, is the basis of dynamic differential scanning calorimetry (DSC). It is possible by means of this method to determine specific heat, glass transition, melting and crystallization processes, thermal effects, purity, polymorphicity, chemical reactions and reaction kinetics. In most cases, a dynamic temperature programme is run through, i.e., the temperature range of interest is covered.
- Comparative Example 2 biodiesel without BHT exhibited the beginning of the strongly exothermic oxidation reaction in the DSC from as low as approx. 60° C.
- Example 1 the biodiesel was analyzed with different BHT additions with the addition of oxygen. These examples show that where as little as 0.1% BHT is added, the oxidation reaction does not set in until 97° C., although it proceeds with a distinctly higher heat production rate. Increasing the amount of BHT to 1% only achieves slight additional stabilization, i.e., the oxidation in this case does not set in until 104° C. A further increase in the amount of BHT to 5% does not cause any increase in the stability.
- the mixture is cooled to room temperature and transferred through a filter and into a 21.5 l metal canister.
- the 20 g/l solution exhibits no cloudiness or precipitation whatsoever even after storage at 0° C. for two weeks.
- FIG. 2 illustrates the result
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A process is described for increasing the storage stability of biodiesel by metering a liquid stock solution which comprises 15 to 60% by weight of 2,6-di-tert-butylhydroxytoluene dissolved in biodiesel into the biodiesel to be stabilized up to a concentration of 0.005 to 2% by weight of 2,6-di-tert-butylhydroxytoluene, based on the overall solution of biodiesel.
Description
- This application is a continuation of U.S. patent application Ser. No. 10/703,263 filed Nov. 7, 2003, incorporated herein by reference.
- 1. Field of the Invention
- The invention relates to a process for increasing the storage stability of biodiesel and more specifically, the invention relates to the use of 2,4-di-tert-butylhydroxytoluene (referred to hereinbelow as BHT) for increasing the storage stability of biodiesel.
- 2. Brief Description of the Invention
- Biodiesel, which is currently being used to an increasing extent to replace petroleum diesel as a fuel for diesel engines, for combined heating and power stations, ships and boats, as well as motor vehicles. Biodiesel comprising of fatty acid alkyl esters, which are predominantly fatty acid methyl esters, is obtained by transesterification, in which vegetable oils such as rapeseed oil, soya oil, palm oils and other vegetable oils used in cooking oil or animal fats, are reacted with methanol in the presence of a catalyst (usually sodium hydroxide solution). Also obtained in addition to the fatty acid methyl esters which can be used as biodiesel is glycerol. This method of preparing biodiesel, known as the CD process, is described in numerous patent applications (DE-A 4 209 779, U.S. Pat. No. 5,354,878, EP-A-56 25 04). Since biodiesel has become ever more important as an alternative fuel for diesel engines, the production of biodiesel has also increased considerably in the last few years.
- Compared to mineral fuels, however, biodesel is disadvantaged by its low storage stability. This is caused by the decomposition of the biodesel's high content of unsaturated fatty esters into short chain products, which reduces the energy value of this alternative fuel. The decomposition leads to precipitation, which is recognizable as cloudiness of the biodiesel. The resulting decomposition products are peroxides, aldehydes and short-chain free fatty acids which form soluble and insoluble polymers as precipitates. The acids tend to corrode injection systems, pumps and nozzles of diesel engines. The insoluble polymers, when crosslinked, can block the nozzles and lead to sparingly soluble deposits. This considerably restricts the functioning of the diesel engines. In addition, soluble and insoluble polymers which are formed by oxidative degradation from the overall decomposition products cause incomplete combustion with soot formation, which can in some cases lead to engine damage. Therefore, none of these decomposition products should be present in the biodiesel. Nonetheless, the increased use of biodiesel as an alternative fuel derived from renewable raw materials makes it absolutely necessary to increase the storage stability of biodiesel.
- It is therefore an object of the present invention to distinctly increase the storage stability of biodiesel, i.e. of fatty acid alkyl esters.
- It has now been found that 2,4-di-tert-butylhydroxytoluene (referred to hereinbelow as BHT), and alternatively known as 2,6-di-tert-butyl-p-cresol, distinctly increases the storage stability of biodiesel.
- The present invention therefore provides a process for increasing the storage stability of biodiesel, in which a liquid stock solution, based on the stock solution, comprises 15 to 60% by weight of BHT dissolved in biodiesel is metered into the biodiesel to be stabilized up to a concentration of 0.005 to 2% by weight of BHT, based on the overall solution of biodiesel.
-
FIG. 1 is a graphical representation of the results of Rancimate test showing addition of increasing amounts of BHT and the percent content of C18 acid methyl ester in the biodiesel correlating to the ppm of BHT added. -
FIG. 2 shows that the difference in cloudiness before (left side) and after addition of BHT (right side). - In the context of this invention, “biodiesel” refers to all saturated and unsaturated fatty acid alkyl esters, in particular fatty acid methyl esters, which can be used as biodiesel fuel, as customarily available under the name biodiesel as a fuel in automobiles for diesel engines in motor vehicles, combined heating and power plants, ships and boats, and other stationary diesel engines. Typically, the fatty acid methyl esters used as biodiesel are C14-C24 fatty acid methyl esters which may be pure or in a mixture. The biodiesels used in the process according to the invention may additionally comprise all customary additives as used, for example, to increase the winter stability of biodiesel. Typically, the biodiesels having storage stability improved by the process according to the invention are prepared by transesterification of methanol with vegetable oils such as rapeseed oil, soya oil, palm oil, used cooking oils and fats or animal fats. The biodiesel which is stabilized in accordance with the invention is preferably that which has been obtained from rapeseed oil or soya oil by the transesterification mentioned above.
- In this context, “storage stability” means reduced cloudiness of the biodiesel, said cloudiness resulting from the reaction of decomposition products formed by oxidative processes in the biodiesel, giving rise to soluble and insoluble polymers which manifest in the form of precipitation.
- The invention further provides a process for preparing a liquid stock solution for use in increasing the storage stability of biodiesel, in which liquefied, optionally distilled, BHT is metered at a temperature in the range from 70 to 120° C., preferably 90 to 120° C., with stirring into biodiesel up to a concentration of 15 to 60% by weight of BHT, based on the stock solution.
- BHT is a solid at room temperature and can only be metered into the biodiesel at room temperature with great difficulty. The inventive stock solution comprising 15 to 60% by weight of BHT, preferably 20 to 40% by weight of BHT, is a highly concentrated solution of BHT in biodiesel which is liquid and meterable and can be very easily metered into the biodiesel to be stabilized. Even after a prolonged period, surprisingly, no precipitation of BHT out of this highly concentrated stock solution can be detected.
- Typically, the stock solution mentioned can be metered into the biodiesel to be stabilized up to a concentration of 0.005% by weight to 2% by weight, preferably 0.1 to 1% by weight, based on the overall solution of biodiesel. It is also possible to add higher concentrations of BHT to the biodiesel. The greatest stability effects are observed up to a concentration of 2% by weight. In comparison to unstabilized biodiesel, the inventively stabilized biodiesel has considerably improved storage stability, i.e., no undesired precipitation of insoluble polymers generated by oxidative degradation is detected in the inventively stabilized biodiesel. In addition, it has been found that BHT advantageously leads to an increase in the solidification point of the biodiesel. In this context, “solidification point” refers to the temperature at which the biodiesel begins to crystallize out.
- The invention further provides the use of BHT for increasing the storage stability of biodiesel by preventing the cloudiness of biodiesel as a result of the decomposition products formed by oxidation processes. The cloudiness manifests itself in the form of precipitation. In accordance with the invention, this precipitation can now be prevented from blocking engine nozzles or generating undesired deposits in the internal engine chamber (pistons, lines) by incomplete combustion, which can lead to engine damage.
- The invention further provides the storage-stabilized biodiesel itself which contains 0.005 to 2% by weight of dissolved BHT.
- The invention is further described by the following illustrative but non-limiting examples.
- Biodiesel (from rapeseed oil) was subjected to a Rancimate test admixed with increasing amounts of BHT (trade product from Bayer AG: Baynox®).
- The Rancimate 679 (Metrohm) consists of a control section and a wet section. In the wet section, the samples are heated and blown through by air in the presence of copper. During the oxidative ageing, short-chain, volatile organic acids are formed and are introduced into a measuring cell filled with distilled water. The conductivity is measured and recorded there continuously.
- The end of the ageing and oxidative stability is indicated by a steep increase in the conductivity. The time until the turning point is reached is referred to as the induction period and serves as a measure for the ageing stability.
- In the examples which follow, all samples were subjected to the same experimental demands.
- Time: 120 minutes at 70° C. while passing through 60 ml/h of air/hour.
- Afterwards, the samples were investigated by GC analysis for their content of unsaturated fatty acid methyl esters. The following table shows the results:
-
Bio- diesel Oil mill Comp. Empty exam- Example Example Example Example Example Rape- ple 1 2 3 4 5 Fatty acid seed oil BHT BHT BHT BHT BHT BHT methyl methyl 0.0% 0.02% 0.04% 0.06% 0.08% 0.1% ester ester by wt. by wt. by wt. by wt. by wt. by wt. C16/ 0.2 0.2 0.2 0.3 0.2 0.3 1× double det. C18/ 21.6 0.4 0.9 2.3 3.7 5.5 11.3 2× double det. C18/ 67.4 43.7 50.8 58.0 60.5 62.7 64.9 1× double det. C22/ 0.2 1.3 1.6 1.7 1.8 1.7 1.7 1× double det. C24/ 0.3 0.3 0.2 0.2 0.2 0.2 1× double -
FIG. 1 shows the results in graphical form. - The results show:
- The higher the content of BHT in the sample was, the greater the proportion of polyunsaturated fatty acid methyl esters. The sample which had not been admixed with BHT exhibits strong degradation of unsaturated fatty acid methyl esters. BHT is able to limit the degradation of unsaturated fatty acid methyl esters in the biodiesel as a function of dose.
- A 5 l flask having a narrow neck was charged with 2 l of biodiesel, and a second flask with the same amount, but admixed with 0.05% of BHT. The vessels were not sealed and left to stand at room temperature with occasional shaking (2-3 times per week). After approximately 6 weeks, the first cloudiness could be observed in the product which had not been admixed with BHT. After a further week, cloudiness as a result of insoluble polymers could be clearly seen.
- In the experiment with the addition of BHT, there was no cloudiness whatsoever as a result of insoluble polymers even after 8 weeks.
- To assess the oxidation stability of biodiesel (from rapeseed oil), the following measurement methods were carried out:
- Biodiesel was investigated using oxygen under pressure (10 bar) by the DSC method (Differential Scanning Calorimetry according to DIN No. 51007). To this end, pure biodiesel and biodiesel with increasing amounts of BHT were used in the test arrangement.
- Determination of the heat flow to a sample, measured relative to a reference sample, both of which are subjected to a defined temperature program, is the basis of dynamic differential scanning calorimetry (DSC). It is possible by means of this method to determine specific heat, glass transition, melting and crystallization processes, thermal effects, purity, polymorphicity, chemical reactions and reaction kinetics. In most cases, a dynamic temperature programme is run through, i.e., the temperature range of interest is covered.
-
-
Beginning Bio- Heating of Energy diesel BHT [% Oxygen rate oxidation released [mg] by wt.]* [mg] [K/min] [° C.] [J/g] Comparative 100 — 10 1 59 490 Example 2 Example 6 100 0.1 10 1 97 510 Example 7 100 1.0 10 1 104 580 Example 8 100 5.0 10 1 104 430 *based on the amount of biodiesel used - When pure oxygen was added (approx. 10 bar) Comparative Example 2 (biodiesel without BHT) exhibited the beginning of the strongly exothermic oxidation reaction in the DSC from as low as approx. 60° C.
- In Examples 1 to 3, the biodiesel was analyzed with different BHT additions with the addition of oxygen. These examples show that where as little as 0.1% BHT is added, the oxidation reaction does not set in until 97° C., although it proceeds with a distinctly higher heat production rate. Increasing the amount of BHT to 1% only achieves slight additional stabilization, i.e., the oxidation in this case does not set in until 104° C. A further increase in the amount of BHT to 5% does not cause any increase in the stability.
- In a two litre stirred flask, 1 500 ml of biodiesel are stirred at room temperature. 300 g of BHT in liquid form are metered in from a dropping funnel heated with steam or water to 80 to 90° C. within 10 minutes, in such a way that the BHT goes immediately into solution.
- Afterwards, the mixture is cooled to room temperature and transferred through a filter and into a 21.5 l metal canister.
- The 20 g/l solution exhibits no cloudiness or precipitation whatsoever even after storage at 0° C. for two weeks.
- 2 l of the same sample of biodiesel were each fed into two different large-volume
- 5 l vessels so that the vessels were each only half-full and the biodiesel had as large as possible a surface area.
- In the vessel P5-0.0, no BHT was added, and in the vessel P5-0.05, 500 ppm of BHT were added.
- After 30 days at room temperature in the closed vessel, distinct cloudiness is observed in the P5-0.0 vessel without BHT addition, said cloudiness being caused by crosslinked insoluble polymers in the biodiesel. In contrast, the biodiesel in the P5-0.05 vessel having 500 ppm of BHT remained completely clear and transparent, and no insoluble polymers whatsoever precipitated out.
-
FIG. 2 illustrates the result. - Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (5)
1. Process for increasing the storage stability of biodiesel, comprising metering a liquid stock solution which, based on the stock solution, comprises 15 to 60% by weight of 2,6-di-tert-butyl-hydroxytoluene dissolved in biodiesel into the biodiesel to be stabilized, up to a concentration of 0.005 to 2% by weight of 2,6-di-tert-butyl-hydroxytoluene, based on the overall solution of biodiesel.
2. Process according to claim 1 , characterized in that the stock solution is metered into the biodiesel up to a concentration of 0.1 to 1% by weight of 2,6-di-tert-butyl-hydroxytoluene, based on the overall solution of biodiesel.
3. Process according to claim 1 , characterized in that the biodiesel is a biodiesel which has been obtained by transesterification with methanol from rapeseed oil, soya oil, palm oil, used cooking oil or animal fat.
4. Liquid stock solution for use in a process for increasing the storage stability of biodiesel, comprising, based on the overall stock solution, 15 to 60% by weight of 2,6-di-tert-butyl-hydroxytoluene dissolved in biodiesel.
5. Storage-stabilized biodiesel, comprising 0.005 to 2% by weight of dissolved 2,6-di-tert-butyl-hydroxytoluene.
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US12/157,692 US20080313956A1 (en) | 2002-11-13 | 2008-06-12 | Process for increasing the storage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel |
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DE10252715.6 | 2002-11-13 | ||
DE10252715A DE10252715A1 (en) | 2002-11-13 | 2002-11-13 | Process for the improving the storage stability of biodiesel comprises addition of 2,4-di-tert-butylhydroxy toluene |
DE10252714A DE10252714B4 (en) | 2002-11-13 | 2002-11-13 | Method for increasing the oxidation stability of biodiesel and the use of mono- or dialkylhydroxytoluene to increase the oxidation stability of biodiesel |
DE10252714.8 | 2002-11-13 | ||
US10/703,263 US20040139649A1 (en) | 2002-11-13 | 2003-11-07 | Process for increasing the storgage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel |
US12/157,692 US20080313956A1 (en) | 2002-11-13 | 2008-06-12 | Process for increasing the storage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel |
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US10/703,263 Continuation US20040139649A1 (en) | 2002-11-13 | 2003-11-07 | Process for increasing the storgage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel |
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US10/703,263 Abandoned US20040139649A1 (en) | 2002-11-13 | 2003-11-07 | Process for increasing the storgage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel |
US12/157,692 Abandoned US20080313956A1 (en) | 2002-11-13 | 2008-06-12 | Process for increasing the storage stability of biodiesel and the use of 2,4-di-tert-butylhydroxytoluene for increasing the storage stability of biodiesel |
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US (2) | US20040139649A1 (en) |
EP (2) | EP1972679B1 (en) |
AT (1) | ATE399834T1 (en) |
AU (1) | AU2003257439A1 (en) |
DE (1) | DE50310078D1 (en) |
DK (1) | DK1563041T3 (en) |
ES (2) | ES2629089T3 (en) |
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PT (1) | PT1563041E (en) |
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DE102005015474A1 (en) | 2005-04-04 | 2006-10-05 | Degussa Ag | Method for increasing oxidation stability of biodiesel, comprises adding a phenyl compound as primary antioxidant to the biodiesel |
DE102005015475A1 (en) * | 2005-04-04 | 2006-10-05 | Degussa Ag | Method for increasing oxidation stability of biodiesel, comprises adding a biphenyl compound as primary antioxidant to the biodiesel |
DE102005048881A1 (en) * | 2005-10-12 | 2007-04-19 | Forschungszentrum Karlsruhe Gmbh | Process for solution crystallization of mixtures |
WO2007079765A1 (en) * | 2005-12-30 | 2007-07-19 | Clean Oil Ag | Vegetable oil diesel fuel |
CA2646216A1 (en) * | 2006-01-04 | 2007-07-12 | Ciba Holding Inc. | Stabilized biodiesel fuel compositions |
SG171626A1 (en) | 2006-02-03 | 2011-06-29 | Eastman Chem Co | Antioxidant compositions useful in biodiesel and other fatty acid and acid ester compositions |
DE102006017105A1 (en) * | 2006-04-10 | 2007-10-11 | Degussa Gmbh | Method for increasing the oxidation stability of biodiesel |
EP1847583A3 (en) * | 2006-04-21 | 2008-11-05 | Infineum International Limited | Improvements in Biofuel |
EP1847584A3 (en) * | 2006-04-21 | 2008-10-22 | Infineum International Limited | Improvements in Biofuel |
CN101535451A (en) * | 2006-07-11 | 2009-09-16 | 英诺斯派克燃料专业有限责任公司 | Stabilizer compositions for blends of petroleum and renewable fuels |
US7901469B2 (en) * | 2006-07-26 | 2011-03-08 | Alternative Fuels Group Inc. | Alternative organic fuel formulations including vegetable oil |
JP2010511067A (en) * | 2006-11-27 | 2010-04-08 | チバ ホールディング インコーポレーテッド | Stabilized biodiesel fuel composition |
GB0714725D0 (en) * | 2007-07-28 | 2007-09-05 | Innospec Ltd | Fuel oil compositions and additives therefor |
US20090094887A1 (en) * | 2007-10-16 | 2009-04-16 | General Electric Company | Methods and compositions for improving stability of biodiesel and blended biodiesel fuel |
EP2174554A3 (en) | 2008-10-09 | 2011-01-12 | Infineum International Limited | Improving the oxidation stability of oils of vegetable or animal origin |
US20120233912A1 (en) | 2011-03-18 | 2012-09-20 | Otkrytoe Aktsionernoe Obschestvo "Sterlitamaxky Neftekhimichesky Zavod" | Antioxidant additive composition, a solution thereof, and a method for improving the storage stability of biodiesel fuel (variants) |
SG193907A1 (en) * | 2011-03-25 | 2013-11-29 | Evonik Oil Additives Gmbh | A composition to improve oxidation stability of fuel oils |
CN103842487A (en) | 2011-03-29 | 2014-06-04 | 富林纳技术有限公司 | Hybrid fuel and method of making the same |
RU2476585C1 (en) | 2012-03-07 | 2013-02-27 | Открытое Акционерное Общество "Стерлитамакский Нефтехимический Завод" | Antioxidant additive composition, solution thereof and method of increasing storage stability of biodiesel fuel (versions) |
EP2895582A1 (en) | 2012-09-13 | 2015-07-22 | Evonik Oil Additives GmbH | A composition to improve low temperature properties and oxidation stability of vegetable oils and animal fats |
AU2015358565B2 (en) | 2014-12-03 | 2020-11-05 | Drexel University | Direct incorporation of natural gas into hydrocarbon liquid fuels |
EP3053992A1 (en) | 2015-02-09 | 2016-08-10 | LANXESS Deutschland GmbH | Biodiesel |
WO2017054921A1 (en) * | 2015-09-30 | 2017-04-06 | Inachem Gmbh | Storage -stable compositions of antioxidants containing ascorbic acid |
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UA86007C2 (en) | 2009-03-25 |
EP1563041A1 (en) | 2005-08-17 |
WO2004044104A1 (en) | 2004-05-27 |
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RU2008126167A (en) | 2010-01-10 |
RU2340655C2 (en) | 2008-12-10 |
AU2003257439A1 (en) | 2004-06-03 |
SI1563041T1 (en) | 2009-02-28 |
RU2005118759A (en) | 2006-01-10 |
DK1563041T3 (en) | 2008-10-20 |
PL376777A1 (en) | 2006-01-09 |
RU2475520C2 (en) | 2013-02-20 |
PT1563041E (en) | 2008-09-25 |
US20040139649A1 (en) | 2004-07-22 |
ATE399834T1 (en) | 2008-07-15 |
PL203138B1 (en) | 2009-08-31 |
EP1972679B1 (en) | 2017-05-10 |
DE50310078D1 (en) | 2008-08-14 |
EP1972679A1 (en) | 2008-09-24 |
ES2629089T3 (en) | 2017-08-07 |
ES2308038T3 (en) | 2008-12-01 |
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