ZA200902834B - Biodiesel purification - Google Patents
Biodiesel purification Download PDFInfo
- Publication number
- ZA200902834B ZA200902834B ZA200902834A ZA200902834A ZA200902834B ZA 200902834 B ZA200902834 B ZA 200902834B ZA 200902834 A ZA200902834 A ZA 200902834A ZA 200902834 A ZA200902834 A ZA 200902834A ZA 200902834 B ZA200902834 B ZA 200902834B
- Authority
- ZA
- South Africa
- Prior art keywords
- water
- membrane
- oil
- phase
- biodiesel
- Prior art date
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- 239000003225 biodiesel Substances 0.000 title claims description 40
- 238000000746 purification Methods 0.000 title claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 239000012528 membrane Substances 0.000 claims description 59
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 35
- 239000003921 oil Substances 0.000 claims description 27
- 235000019198 oils Nutrition 0.000 claims description 27
- 230000002209 hydrophobic effect Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 235000019499 Citrus oil Nutrition 0.000 claims description 18
- 239000010500 citrus oil Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 230000005012 migration Effects 0.000 claims description 4
- 238000013508 migration Methods 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 230000036983 biotransformation Effects 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 239000002569 water oil cream Substances 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 101100421131 Caenorhabditis elegans sek-1 gene Proteins 0.000 claims 1
- 239000012071 phase Substances 0.000 description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229940057995 liquid paraffin Drugs 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 238000010954 commercial manufacturing process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000010461 other edible oil Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
oo J ) FIELD OF THE INVENTION
This invention relates to the separation of water-soluble components (including water itself) and oil-soluble components (including oils themselves) from one another. The water-soluble and oil-soluble components to be separated can comprise or be present in pure solutions, stable suspensions (for example emulsions) or unstable suspensions (for example two phase mixtures. There are many examples of such components, a typical example of which is the mixture of components obtained following the transesterification reaction in the production of biodiesel.
BACKGROUND OF THE INVENTION L =
It is often necessary to separate water and/or water-soluble salts and other water- soluble impurities from oil-soluble components (including hydrophobic oils themselves).
It is further often necessary to separate oil and/or oil-soluble components from water- soluble components (including hydrophilic water itself).
A simple method of removing water-soluble components from an oil phase is to add water, shake to promote intimate contact between the two phases, and allow the phases to separate by gravity settling and decanting or centrifuging. This is tedious and requires that it is physically possible to separate the two phases (for example, impossible if the two phases have the same density or form a stable emulsion). Often, after separating the two phases, there is a small residual amount of the water phase in the oil phase and a small residual amount of the oil phase in the water phase which is undesirable in many circumstances. Furthermore, if the oil phase (ideally without water-soluble components) is the final product, some product is lost to the water phase in this simple method. One such circumstance arises from the manufacture of biodiesel! from triglycerides (such as soybean and other edible oils). The process involves a transesterification reaction that results in the production of glycerol as a by-product.
Although it is possible to separate the majority of the glycerol from the biodiesel by gravity settling or centrifugal action some residual glycerol and other impurities remain in
PN
- the biodiesel phase. Moreover, the biodiesel phase is contaminated by a small amount ’ of aqueous phase due to the presence of emulsions and an imperfect phase separation.
Glycerol therefore is a water soluble impurity present in the oil- (ie., biodiesel-) phase because glycerol is slightly soluble in the resulting fatty acid methyl or ethyl ester constituting the biodiesel. Other water-soluble impurities such as free fatty acids, salts thereof and water itself are also present in the biodiesel and it is important to remove all these impurities along with the glycerol.
If glycerol is to be produced as a co-product in the manufacture of biodiesel it is also
Important to remove the traces of biodiesel from the glycerol as this has to be of high : purity if itis to be used in the cosmetic and pharmaceutical fields. The presence of ¥ biodiesel, which also has a high boiling point, renders distillation somewhat difficult. In this case, biodiesel is an oil-soluble impurity present in a hydrophilic phase.
Another application of the invention will be directed to the removal and isolation of citrus oils from a water / citrus oil mixture such as is obtained in the initial processing of citrus fruit for the production of citrus oil. In this case the citrus oil is an oil-soluble component present in a predominantly aqueous phase. The invention described herein replaces the traditional and costly method of centrifugation as a means of separating the valuable citrus oil component from water.
It is an object of the present invention to provide a novel process for the separation of the products mentioned above that is more efficient than standard processes such a distillation, steam distillation, settling, centrifugation and other well-known methods.
It is a further object of the invention to provide a separation method that can be used during the transesterification reaction that results in improved yields of the final products and in improved purity.
According to the invention a method of separating water-soluble components (including water itself) and oil-soluble components (including oils themselves) from one another
- 7 J ’ - includes the step of circulating water or a hydrophilic phase possibly containing oil- ’ soluble components, on one side of a hydrophilic or hydrophobic porous membrane and circulating an oil or hydrophobic phase possibly containing water-soluble components on the other side under conditions to promote mass transfer of the various components to the desired side of the membrane; and thereby separating substantially all the hydrophilic components from all the hydrophobic components.
It may be important to create and sustain a pressure gradient across the membrane depending on the products concerned.
In one form of the invention, as applied to the purification of biodiesel, the membrane is hydrophobic, so that the biodiesel remains on its side but wets the membrane pores by capillary action. Water on the other side of the membrane contacts the biodiesel phase at the surface of the pore so that water and the preferentially water-soluble substances migrate into the water phase and coincidentally any biodiesel in the water phase migrates into the biodiesel phase.
A hydrophilic membrane will cause migration of these same components in the same direction with the pores of the membrane being wetted by the water.
In another form of the invention, as applied to the isolation of citrus oils from a water-oil emulsion, a hydrophobic membrane is used, and purified citrus oil is circulated on one side of the membrane coincidentally wetting the pores of the membrane by capillary action. A mixture of water (predominantly) and citrus oil on the other side of the membrane contacts the citrus oil phase at the surface of the pore so that citrus oil migrates into the citrus oil phase thereby adding to the volume of citrus oil recovered in pure form.
It has been found in the above applications that the migration is improved if the two phases are circulated tangentially to the surface of the membrane.
In other processes, such as the enzyme biotransformation of triglycerides, involving the production of glycerol that inhibit the transesterification reaction, the water-soluble
- glycerol causing the aforementioned inhibition can be continuously removed as it is ’ produced, thereby facilitating the process.
Apart from replacing the traditional “mix and shake” methods of contacting the two phases, and replacing expensive high-speed rotating centrifugal contactors and expensive pumps, the present invention provides a great improvement in separating water-soluble and oil-soluble components from one another in a two phase system.
An embodiment of the invention is described below with reference to the accompanying diagrams and examples: a
In Figure 1, an oil phase containing water-soluble components (for example, a
BIODIESEL FEED containing free fatty acids) is introduced from the top left into a FEED
TANK, as shown. From this tank the biodiesel is pumped with pump P1 into a
MEMBRANE CONTACTOR thereby passing the oil phase tangentially across the surface of either a hydrophobic or hydrophilic MEMBRANE. The oil-phase exits the
MEMBRANE CONTACTOR and is returned to the FEED TANK thereby completing the hydraulic circuit. The oil-phase is pumped around the circuit continuously. Note that this hydraulic circuit might include various pressure and flow instrumentation and control hardware for the beneficial monitoring and control of pressure and flow within the circuit.
Note also that the MEMBRANE inside the MEMBRANE CONTACTOR divides the
MEMBRANE CONTACTOR into two compartments. Water-soluble components migrate from the oil phase to the water as shown in Figures 2 and 3 in the case of hydrophobic : and hydrophilic membranes, respectively. Once the BIODIESEL FEED in the FEED
TANK is sufficiently pure it can be removed from the FEED TANK as PURIFIED
PRODUCT. The introduction of BIODIESEL FEED and the removal of PURIFIED
PRODUCT can also take place simultaneously as is well-known in the chemical engineering art.
Simultaneous with the circulation of the oil-phase as described above, water is pumped from a WATER TANK with pump P2 into a MEMBRANE CONTACTOR thereby passing the water tangentially across the opposite side of either a hydrophobic or hydrophilic
} { - MEMBRANE. The water phase now containing water-soluble components exits the ’ MEMBRANE CONTACTOR and is returned to the WATER TANK thereby completing the hydraulic circuit. The water phase is pumped around the circuit continuously, and the circuit might include various pressure and flow instrumentation and control hardware for the beneficial monitoring and control of pressure and flow within the circuit. The water phase now containing water-soluble components can be discarded and replaced with FRESH WATER or circulated back around to pick up additional water-soluble components. The introduction of FRESH WATER and the removal PURGE WATER can be done either batch-wise or continuously as is well-known in the chemical engineering art. & Such MEMBRANE CONTACTORS are commercially available and are manufactured, : for example, by Membrana, a division of Celgard Inc under the trade mark Liqui-Cel.
These contactors are primary designed for solvent extraction in various appropriate : sizes.
f ~ Example 1 — A purifier system was set up as depicted in Figure 1. Specifically, the membrane - contactor employed was a Liqui-Cell™ 4” diameter contactor with %” NPT female connections and fitted with a Kalrez™ seal option to resist attack by hydrophobic chemical solvents. The membrane contactor was supplied by Membrana in Charlotte, North Carolina, U.S.A. Materials of construction for the membrane contactor and membrane material were polypropylene and polyethylene making the membrane itself hydrophobic. The membrane configuration was of the shell and lumen type featuring lumen fibers with 0.03 micron pores and a 240 micron lumen |.D. Total membrane area of the contactor was 210 fi. Maximum temperature and pressure limits for the contactor were 104 degrees F and 45 psig, but the system was run at ambient temperature with pure liquid paraffin on the oil side and pure water on the water side. Pressure in the water recirculation loop varied between about 5 and 15 psig, and pressure in the oil loop varied between about 5 and 10 inches of mercury vacuum owing to recirculation pump P1 located downstream of the membrane contactor. The pressure differential across the membrane measured by instrument DPT in Figure 1 advantageously prevented liquid paraffin from seeping through the membrane and contaminating the water side. Recirculation flow rates for both hydraulic circuits were in the range of between about 5 and 10 liters per minute. No automatic control of pressure was implemented.
Piping for the purifier set up was designed to be chemically compatible with both the aqueous and organic streams. Materials of construction included polypropylene, high density polyethylene, stainless steel polysulfone, Teflon™, EPDM, and Teflon-coated Viton™.
During the course of operations, the pure water became inadvertently contaminated with liquid paraffin for reasons unrelated to the operation of the purifier system. The resultant stable emulsion of small liquid paraffin droplets dispersed in the water phase now present on the water side of the system depicted in Figure 1 was cloudy and had the characteristic odor of liquid paraffin. Pure liquid paraffin continued to circulate on the oil side of the system. Note that in this scenario, the purifier system, according to the invention reported herein, could be expected to separate oil-soluble components (liquid paraffin) present as contaminants in a circulating hydrophyllic phase from the bulk hydrophyllic phase by the means of circulating the emulsion on one side of a hydrophobic porous membrane and circulating a hydrophobic phase (pure liquid paraffin) on the other side. Mass transfer of oil-soluble contaminants from the water side to the oil side could be expected to separate substantially all the hydrophilic components from all the hydrophobic components.
The system was allowed to run overnight under the conditions described above. In the morning the water side of the system was completely free of liquid paraffin contamination judging by the water-white clarity of the liquid circulating on the water side and judging by the absence of any characteristic odor of liquid paraffin.
Example 2 — A purifier system was set up as depicted in Figure 1. Specifically, the membrane contactor employed was a Liqui-Cell™ 2%" diameter x 8” long contactor with 1/4” NPT female connections and fitted with a Kalrez™ seal option to resist attack by hydrophobic chemical solvents.
The membrane contactor was supplied by Membrana, a Division of Celgard, Inc. in Charlotte, North
Carolina, U.S.A. Materials of construction for the membrane inside the contactor were such that the membrane itself was hydrophobic. Maximum temperature and pressure limits for the contactor were 104 degrees F and 45 psig. The system was run at ambient temperature with partially purified
BioDiesel (i.e., methyl esters of predominantly C,s and C,; fatty acids) on the oil side and pure water on the water side. The partially purified BioDiesel was obtained by sampling a commercial manufacturing process just prior to the final water washing purification steps. This partially purified BioDiesel so- obtained contained a variety of water soluble contaminants. Pressure in the water recirculation loop varied between about 1 and about 5 psig, and pressure in the oil loop varied between about 5 and 10 inches of mercury vacuum owing to recirculation pump P1 located downstream of the membrane contactor. The resulting pressure differential across the membrane advantageously kept BioDiesel on the oil side of the hydrophobic membrane and water on the water side of the hydrophobic membrane.
g Recirculation flow rates for both hydraulic circuits were in the range of between about 100 and 300 - milliliters per minute. No automatic control of pressure was implemented. : Piping for the purifier set up was silicone tubing which was chemically compatible with both the aqueous and organic streams. Recirculation pumps were miniature positive displacement gear pumps with a variable speed drives so that recirculation flow rates could be adjusted.
The partially purified BioDiesel circulating on the oil side of the system was in some instances further contaminated with compounds known to be soluble in both water and BioDiesel such as sodium n- dodecyl sulfate or acetic acid. Sodium concentration in the partially purified BioDiesel was measured by atomic adsorption spectrometry (38.9 parts per million), and acetic acid concentration was measured by gas chromatography (about 0.5 area percent of the total spectrum).
During operation of the purifier system water-soluble components (sodium-containing compounds or acetic acid) migrated from the BioDiesel phase to the water phase in sufficient amounts that mass transfer coefficients could be calculated from the time-dependent reduction in the concentration of water-soluble components in the BioDiesel. The following equations were employed to calculate the . mass transfer coefficients.
J (flux) = (KA) oivwater * { [Xoi = Aoiliwater ® [XJwater } where
J is flux with units of milligrams x / time. (KA)ow is a lumped parameter inversely related to mass transfer resistance across the membrane separating the oil and water phases with units of liters/min.
K is related to a mass transfer coefficient and is affected by cross flow velocity, viscosity, solution chemistry and other liquid phase effects on both sides of the membrane.
A is membrane area. Note, however, that KA is measured as a lumped parameter. : Yow iS the distribution coefficient between the oil and water phases and depends on the chemical activity of x in each of the phases at equilibrium. [x] is the titer of the water-soluble component of interest in either the BioDiesel or the water.
During the migration of water-soluble components from the BioDiesel phase to the water phase,
In { ait) — [Xl } — In { [Xai’(t) — [XJoi™ } = Bet where
B = (KA)aiswater | Vai + (KA)oivwater * Yoivwater | Viater with superscripts “0” and “eq” refering to initial and equilibrium conditions and V referring to the volume of either the oil (BioDiesel) or the water phase. :
After about 24 hours, the concentration of sodium in the partially-purified BioDiesel dropped from 38.9 ppm to about 10 ppm. In a separate experiment, the concentration of acetic acid in the partially-purified
BioDiesel dropped from about 0.5 area percent to less than 0.15 area percent of the total chromatogram in about 12 hours. Resultant lumped mass transfer coefficients, (KA)qisater, Were on the order of about 0.05 liter/min.
Claims (11)
1. A method of separating water-soluble components (including water itself) and oil-soluble components (including oils themselves) from one another including the step of circulating water or a hydrophilic phase on one side of a hydrophilic or hydrophobic porous membrane, and circulating an oil or hydrophobic phase on the other side under conditions to promote mass transfer of the various components to the desired side of the membrane; and separating substantially all the hydrophilic components from all the hydrophobic components.
. 2 } Bi
2. The method according to claim 1 in which the water or hydrophilic phase contains oil- soluble components.
3. The method according to claim 1 or 2 in which the oil or hydrophobic phase contains one or more water-soluble components.
4. The method according to any of the above claims including the step of creating and sustaining a pressure gradient across the membrane.
5. The method according to any of the above claims, as applied to the purification of biodiesel, in which the membrane is hydrophobic, so that the biodiesel remains on its side but wets the membrane pores by capillary action, while water on the other side of the membrane contacts the biodiesel phase at the surface of the pore for the water and substances migrate into the water phase, and coincidentally any biodiesel in the water phase migrates into the biodiesel phase.
« Sue : ’ /
a
6. The method according to claim 5 in which the membrane is hydrophilic and causes migration of these same components in the same direction, with the pores of the membrane being wetted by the water.
7. The method according to any of the above claims as applied to the isolation of citrus oils : from a water-oil emulsion including the use of a hydrophobic membrane, the purified citrus oil being circulated on one side of the membrane coincidentally wetting the pores of the membrane by capillary action; and a mixture of water and citrus oil on the other side of the membrane contacts the citrus oil phase at the surface of the pores so that citrus oil migrates into the citrus oil phase. 5
8. The method according to any of the above claims in which the two phases are circulated tangentially to the surface of the membrane.
9. The method according to any of claims 1 to 4 as applied to the enzyme biotransformation of triglycerides, involving the production of glycerol that inhibits the transesterification reaction, in which the water soluble glycerol causing the aforementioned inhibition is continuously removed as it is produced.
10. A method of separating water or water-soluble components and oil or oil-soluble - components substantially as described in the drawings, and examples.
11. Apparatus for carrying out the method of any of the above claims substantially as described with reference to the drawings.
0 / f Dated this 23 day of April 2009 7 MORRISON FORSTER INC.
APPLICANTS’ PATENT ATTORNEYS
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA200902834A ZA200902834B (en) | 2008-01-24 | 2009-04-23 | Biodiesel purification |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA200800752 | 2008-01-24 | ||
| ZA200902834A ZA200902834B (en) | 2008-01-24 | 2009-04-23 | Biodiesel purification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200902834B true ZA200902834B (en) | 2010-07-28 |
Family
ID=42738938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200902834A ZA200902834B (en) | 2008-01-24 | 2009-04-23 | Biodiesel purification |
Country Status (1)
| Country | Link |
|---|---|
| ZA (1) | ZA200902834B (en) |
-
2009
- 2009-04-23 ZA ZA200902834A patent/ZA200902834B/en unknown
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