Recovery of chroman derivatives

Details Recovery of chroman derivatives Recovery of chroman derivatives

2001-07-25

2002-06-11

Powers, Fiona T. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C549S201000, C549S413000

Reexamination Certificate

active

06403811

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to a method of recovering a concentrate of chromans from a mixture containing chromans.
BACKGROUND TO THE INVENTION
The chromans are a commercially valuable group of chemicals that show biological activity as vitamin E and antioxidant properties. In this specification and the claims, the term “chromans” includes chroman and derivatives of chroman such as the hydroxy chromans tocopherol and tocotrienol (commonly referred to as the “tocols”), the alpha, beta gamma and delta forms corresponding to 3,2,1 and 0 methyl groups. They are often used as dietary supplements. Chromans are second tier free radical scavengers in animals and humans which work with vitamin C and ubiquinone to minimize oxygen damage to cells.
Chromans are present in many natural lipids. Chroman concentrates are prepared from the “distillate” created while deodorising the lipids. Lipids are deodorised using a distillation process designed to remove volatile products. The volatile products are principally free fatty acids, but also include aldehydes from oxidation and many other substances. The molten lipid is either purged with super heated steam injection or spread on a large surface in a flowing steam flux. The volatiles (including the chromans) and the steam are then condensed and the non-aqueous fraction recovered as the “distillate”.
Presently, the main source of vitamin E is RRR-&agr;-tocopherol derived from soybean oil. The raw oil is stripped with steam to strip the lower molecular weight free fatty acid (“FFA”) from the oil which has a molecular weight three times that of the FFA. The chromans have a similar molecular weight to the FFA and therefore follow the FFA into the distillate. The distillate is then redistilled to give a higher concentration of chromans. Typically, the chromans must then be methylated to give vitamin E.
There are two main problems with the known process. First, if there is a low concentration of chromans, the relative vapour pressure between the chromans and the FFA in the distillate is insufficient to enable satisfactory concentration. Second, during the distillation a high concentration of tocotrienols, phytol and farnesene form and these compounds have a low vitamin E activity. Further, the process based on a series of distillations is inefficient and uses a lot of energy and capital plant.
As a result, investigations were made into developing a process to concentrate chromans which avoids the high temperature refining process.
There is a well known art for concentrating hydrophobic molecules from high surface tension bulk liquids such as water by using froth flotation. However, this art is not applicable to “distillates” which are mainly C
18
-C
22
FFA, because detergents suitable for aqueous systems do not stabilise a froth of FFA. The chromans present in the distillate do not significantly accumulate on the air/fatty acid interface as both molecules have similar surface properties in the FFA phase.
Therefore, further investigations were made into the possible use of froth concentration to achieve a chroman concentrate.
DESCRIPTION OF THE INVENTION
It was found that the chromans can be concentrated by froth flotation if the chromans were activated by phosphorylation. The phosphorylated chromans are insoluble in the FFA and form a brittle froth that contains a higher concentration of chromans than the FFA phase.
Accordingly, a process of recovering a concentrate of chromans from a distillate containing chromans is provided comprising the steps of:
(1) forming chroman phosphates in the distillate;
(2) subjecting the distillate containing chroman phosphates to shearing forces, in the presence of a gas of flotation to form a froth; and
(3) recovering the froth containing the concentrate of chroman phosphates.
In one preferred form, the froth could be further stabilised by additions of small quantities of silicone surfactant and water. Preferably, the silicone surfactant concentration is between 0.01 to 0.0001%.
The froth could also be further stabilized by the addition of a sugar such as glucose. The sugar is added to complex with the chroman phosphates and would typically be present in a mole ratio to the chromans of 0:1 to 2:1. The froth can also be stabilized by forming a chroman phosphate salt with sodium or potassium.
Any convenient method of phosphorylation can be used to form the chroman phosphates. Typically, the phosphorylation is performed by addition of excess of poly phosphoric acid (eg about 50% mole excess), with strong stirring to generate an emulsion in the molten fatty acid. The phosphorylation reaction may be further enhanced by the addition of a soap such as sodium oleate (eg three moles of soap relative to the poly phosphoric acid), then by allowing the reaction to proceed for 15 to 45 minutes (preferably about 30 minutes). The addition of a soap increases the solution concentration of the reagent.
Preferably, the chromans are phosphorylated using P
4
O
10
as per the method disclosed in Australian provisional patent application PQ0374 (International Publication Number WO 00/69865) at a temperature at which the FFA is liquid. The contents of Australian provisional patent application PQ0374 (International Publication Number WO 00/69865) are hereby incorporated by reference. The P
4
O
10
is used in equal mole ratio to chromans. Typically, the amount of chromans is 1% of distillate.
Preferably, the temperature at which the process is carried out varies from the melting point of the “distillate” to about 200° C.
The gas of flotation used in the process is preferably air, but other gases inert to the process may be used. For example carbon dioxide or nitrogen gas would be suitable as gases with limited solubility but yet capable of generating bubbles where there is a finite surface tension at the gas/liquid interface.
Preferably, the shearing forces are applied using an aerator. The aerator must be capable of generating a stream of bubbles of no more than 3 mm diameter. In this respect, the aerator will give shear sufficient to intimately mix the distillate with the chemical additives. Standard aerators used for froth flotation are not suitable for viscous material.


REFERENCES:
patent: 3212901 (1965-10-01), Robeson
patent: 0 171 009 (1986-02-01), None
patent: 0 338 429 (1989-10-01), None
patent: 0 641 790 (1995-03-01), None
patent: WO 00/69865 (2000-11-01), None
Xiandai Huagong, (1987), 17(7), Lei, Bingfu and Sun, Dengwen “Progress in alpha-tocopherol preparation technology”, & Chemical Abstracts #129:113349. See whole abstract.
Arq.Biol.Technol. (1994), 37(4) , 1003-1011, Almeida, Mem et .al., “Evaluation of soybean oil deodorization distillate for Vitamin E recovery”, & Chemical Abstracts #123:142172. See Whole document.
Biosci.Biotechnol.Biochem., 62(12), 2463-2466, 1998, Miyamoto, S. et al., “Synthesis of a Novel Phosphate Ester of a Vitamin E Derivative and Its Antioxidative Activity”, & Medline Abstract #1999138223. See abstract and p. 2463 column 1, line 12.
JP 53015381 (EISAI Co. Ltd.) Feb. 13, 1978, & Patent Abstracts of Japan #10045783. See whole abstract.
JP 10045783 (Showa Denko KK) Feb. 17, 1998, & Patent Abstracts of Japan #10045783. see whole abstract.

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