WO2007045057A2

WO2007045057A2 - Process for extraction of carotenoids

Info

Publication number: WO2007045057A2
Application number: PCT/BR2006/000215
Authority: WO
Inventors: Octávio Augusto Ceva ANTUNES; Donato Alexandre Gomes Aranda; Lucio Cardozo Filho
Original assignee: Universidade Federal Do Rio De Janeiro-Ufrj
Priority date: 2005-10-18
Filing date: 2006-10-17
Publication date: 2007-04-26
Also published as: BRPI0504594A; WO2007045057A3

Abstract

The presente invention is related to new techniques for the extraction of carotenoids, preferably beta-carotene, from solid residues or 'husks' coming from the processing of palms. This technique is based on the use of organic and inorganic solvents such as carbon dioxide (CO2) and/or light hydrocarbons.

Description

PROCESS FOR EXTRACTION OF CAROTENOIDS

Field of the Invention

The current invention is related to new techniques for the extraction of carotenoids, preferably beta-carotene, as from solid residues or "husks" coining from processing of palms . Background to the invention

Carotenoids are the pigments that go from yellow to red and that are widely distributed amongst plants. Around 50% of these may potentially supply vitamin A activity, being referred to as pro-vitamin A carotenoids.

Beta-carotene, one of more than 600 carotenoids existing in nature (see figure 1) is the most abundant and the most efficient pro-vitamin A present in our food. Theoretically a molecule of beta-carotene can be split into two vitamin A molecules. However in the middle of the body, beta-carotene is only partially converted to vitamin A, the rest being stored. Being a pro-vitamin, beta- carotene is converted slowly, controlled by the level of vitamin A, therefore not causing toxicity

Within the inventions related to the process of the extraction of carotenes are found the following patents: Heidlas et al 3 Feb 1998 (US 5,714,658), Nonomura et al, 14 JuI 1987 (US 4,680,314) and Peter et al 18 Jun 2002 (US 6,407,306). In Heidlas' s invention the method is to use steres of acetic acid in the extraction of carotene from natural sources. In Nonomura et al's (1987) invention the authors extracted comestible oil using algae. In a more recent work, Peter et al (2002) applied different substances like acetonitrilla, N-metil-pirrolidona etc to the extraction of carotenes as from biological fats and oils .

Other documents related to this theme also can be cited; GB1562794, published on 19/03/1980 that deals with a method for extraction of carotenes from palm oil; IN184306, published on 5/8/2000 that deals with another process which isolates carotenes from crude palm oil; CZ20003557, published on 14/3/2001 that deals with another process for the extraction of carotenes. A Brazilian patent order PI0212639-7, deposited on 4/9/2002 by Lycord Natural Products Industries Ltd deals with a process to extract carotenes from vegetable material containing carotenes covering the following stages: (i) mix the plant material with water until a Brix is ^" reached; (ii) compress the mixture at. this stage and (i) separate the solids from the liquid in order to obtain two phases, pulp and serum; and

(ii) extract the pulp to obtain oleoresin from the plant containing carotenoid. As can be verified, just by citing documents dealing with the same theme, none of them went into the invention that will be described here deeply. Brief description of the figures

Figure 1 shows the molecular structure of the . different kinds of carotenoids.

Figures 2 and 3 show, as examples, the results of qualitative spectr-ophotometric analyses on the UV-Vis of the extracts obtained from the extractions with different solvents, inorganic and organic. Both figures show spectra with similar profiles and absorptions in a maximum intensity around 450 nm corresponding to beta-carotene.

Figure 4 shows the results of solubility of beta- carotene in pure CO₂ as a function of the density of the CO2. It can be observed that in general, the solubility increases with temperature and the CO₂ density. Description of the invention

The increasing use of bio-renewable agricultural cultures, like palms for example, in the production of vegetable oils has propelled various sectors.

The possibility of recuperation of substances frequently used in pharmacies as from "husks" or fiber coming from processing is very interesting. In the case of the palm, it is possible by means of techniques described here, to extract carotenoidsy ^'. preferably beta-carotenes from a solid sub-product or fiber which turns such a process very attractive economically, since using one is using a sub-product to obtain substances with a high added value. The current invention uses as solvents in the extraction process of carotenes from the "husks" of palm fruit, inorganic composts, preferably carbon dioxide (CO₂) Inorganic, and also organic, preferably ethylene, n-propane and/or n-butane in different temperature and pressure . conditions, including super-critical ones.

In the process the fibers are initially dried in a hothouse with re-circulating air at a temperature preferably between 30 and 60° C and for a time of between 10 to 180 minutes. After drying the extractor is loaded with dry palm fibers, the temperature is defined as from a controlled bath.

In following the extractor is pressurized to the desired pressure, keeping it for as a sufficient time, preferably between 40 and 180 minutes with an aim at reaching the maximum solubility per part of the solvent used.

The solid residue is discarded after this stage and the extract (for example, mixture of oil and β-carotene) analyzed immediately through photospectometry in the uv-vis. The extraction time using solvents in the "super-critical" states varied between, preferably, 30 and 180 minutes. The photospectometric qualitative analyses in the uv-vis in the extracts obtained from extraction with various solvents are shown in Figures 2 and 3. We highlight, that the samples relative to these analyses had to be diluted due to the high concentrations.

Examples of concretizations using pure CO2 as a solvent or in conjunction with ethylene for the extraction of beta-carotene will be described below.

Example 1 — Extraction of beta-carotene using pure CO2 as a solvent.

An example of concretization of the extraction process . using pure C02 as a solvent was obtained using 100 grams of

"husks" that were dried in a hothouse with re-circulation of air at a temperature of 45° C for 20 minutes, being taken to an extractor at a temperature of 40° C for a period of 2 (two) hours at a carbon dioxide pressure of 250 bars .

As from the solution extracted (oily mixture) a solution of lesser concentration was prepared in chloroform/cyclohexane (1:10) for UV-VIS photospectrometric analysis .

Example 2 - Extraction of beta-carotene using pure ethylene as a solvent

Another form of extraction of . beta-carotene, as ^• from palm fiber is obtained using pure ethylene as a solvent.

In this case 100 grams of "husks" were used that were dried in a hothouse with re-circulation of air at a temperature of 45° C for 20 minutes, being taken to an extractor at a temperature of 40° C for a period of 1 (one) hour at an ethylene pressure of 150 bars.

As from' the solution extracted (oily mixture) a solution was prepared for UV-VIS photospectrometric analysis .

Example 3 - Extraction of beta-carotene using ethylene combined with CO₂ as solvents.

100 grams of "husks" were dried in a hothouse with recirculation of air at a temperature of 45° C for 20 minutes, being taken to an extractor at a temperature of 40° C for a period of 1 (one) hour at an ethylene pressure of 150 bars.. After the extraction with ethylene extraction with CO₂ was done using the same extract from the previous phase. As from the extracted solution (oily mixture) a solution was prepared for UV-VIS photospectrometric analysis. Table 1 shows the yields from the tests of extraction of beta-carotene using different solvents, both organic and inorganic in different pressure, temperature, time conditions etc. As from the table below it can be seen that a greater yield (%) in extracted oil mass (organic phase in which the beta-carotene is found) is had when using n- butane as a solvent, also in this case, needing a lesser volume of solvent .

Table 1

Solvents

CO2 Ethylene n-Butane

Extraction 2 2 1 1 time (h)

Pressure (bar) 250 255 150 80

40 60 40 40

Extraction temp. (⁰C)

Solvent vol. 307.7 156.8 75.55 53.53

(cm³)^'

Extract mass 30,69 24.71 20.12 12.92

(g)

Obtained oil 0.2364 0.1579 0.12 0.1240 mass (g)

Yield (%) 0.77% 0.64% 0.61% • 0.96%

Claims

1. Process of extraction of carotenoids from solid residues characterized by using organic and inorganic compound solvents jointly or separately.

2. Process according to claim 1, characterized by using as extraction solvents, preferably carbon dioxide (CO2) and light hydrocarbons.

3. Process according to claim 1, characterized by the fact of using "husks" or fiber coming from palm processing with solid residues.

4. Process according to claim 1, characterized by being conducted in different time, temperature and pressure conditions, including supercritical ones.

5. Process according to claim 1, characterized by the solid residues being dried at .a temperature, preferably, between 30 and 60° C and for a time period, preferably between 10 and 180 minutes.

6. Process according to claim 5, characterized by using preferably a hothouse with re-circulation of air.

7. Process according to claim 4, characterized by the fact of having used, preferably, an extractor.

8. Process according to claim 4, characterized by the fact of the temperature of the system being defined by a controlled bath.

9. Process according to claim 4, characterized by being conducted at pressures, preferably between 50 and 300 atm.

10. Process according to claim A₁ characterized by- being conducted in a period preferably between 40 and 180 minutes .

11. Process according to claim 1, characterized by the extract being analyzed by mean of UV-VIS photospectrometric analysis .

12. Process according to claim 2, characterized by the fact of the hydrocarbons having from 1 to 4 carbon atoms

13. Process according to any of the previous claims, characterized by being conducted in a large quantity or in a continuous system.