PREPARATION METHOD FOR POLYUNSATURATED FATTY ACID-CALCIUM

Abstract

The present invention relates to a preparation method for a polyunsaturated fatty acid-calcium, primarily comprising directly reacting a polyunsaturated fatty acid material with a water-soluble calcium compound to obtain a polyunsaturated fatty acid-calcium salt. The present invention has a simple technical process, short reaction time, and high reaction yield. The produced polyunsaturated fatty acid-calcium product is of high quality, and relatively less byproducts and waste water are produced. The process is overall environmentally friendly and has small safety risks, and is suitable for scaled production.

Claims

1. A method of preparing a polyunsaturated fatty acid-calcium, comprising the following step: (i) dissolving a water-soluble calcium compound material or a mixture of several water-soluble calcium compound materials in an appropriate amount of water, to obtain an aqueous solution of calcium compound; (ii) adding the aqueous solution of calcium compound to a polyunsaturated fatty acid material at −20˜100□ of temperature; the polyunsaturated fatty acid material comprises one or more of the following substances: a polyunsaturated fatty acid with a formula ##STR00004## wherein R.sub.1 is a C.sub.6˜C.sub.40 alkenyl group, R.sub.2 is H or a C.sub.1˜C.sub.4 alkyl group; and a polyunsaturated fatty acid with a formula ##STR00005## wherein R.sub.3, R.sub.4, R.sub.5 are a hydroxyl or a C.sub.1˜C.sub.4 carboxylic acid group or a C.sub.6˜C.sub.40 carboxylic acid group containing one or more double bonds; R.sub.3, R.sub.4 and R.sub.5 can be the same or different; and R.sub.3, R.sub.4 and R.sub.5 cannot be simultaneously a hydroxyl group or a C.sub.1˜C.sub.4 carboxylic acid group; (iii) filtrating to obtain a solid of polyunsaturated fatty acid-calcium after completion of the reaction; and (iv) drying and crushing the solid of polyunsaturated fatty acid-calcium, to obtain a free-flowing polyunsaturated fatty acid-calcium product.

2. The method according to claim 1, wherein the polyunsaturated fatty acid material is selected from the group consisting of free-type polyunsaturated fatty acid, methyl ester-type polyunsaturated fatty acid, ethyl ester-type polyunsaturated fatty acid, and glyceride-type polyunsaturated fatty acid.

3. The method according to claim 2, wherein the polyunsaturated fatty acid material is selected from the group consisting of fish oil, algae oil, linoleic acid, conjugated linoleic acid, linolenic acid, and arachidonic acid.

4. The method according to claim 1, wherein the content of the polyunsaturated fatty acid in the polyunsaturated fatty acid material is 10˜100 wt %.

5. The method according to claim 1, wherein the water-soluble calcium compound material is selected from the group consisting of calcium acetate, calcium lactate, calcium chloride, calcium nitrate, calcium citrate, and calcium fumarate.

6. The method according to claim 5, wherein the molar quantity of the water-soluble calcium compound material is 0.1˜0.9, relative to a molar equivalent of the polyunsaturated fatty acid.

7. The method according to claim 6, wherein the molar quantity of the water-soluble calcium compound material is 0.5˜0.7, relative to the molar equivalent of the polyunsaturated fatty acid.

8. The method according to claim 6, wherein the water weight of dissolving the water-soluble calcium compound material is 1˜40, relative to the weight equivalent of the water-soluble calcium compound material.

9. The method according to claim 1, wherein the reaction temperature is −20˜100□, and preferably, the reaction temperature is 20˜100□.

10. The method according to claim 9, wherein the reaction time is 0.5˜10 hours, and preferably, the reaction time is 0.5˜3 hours.

Description

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS THEREOF

[0042] Hereafter, the present invention will be described specifically with reference to the examples. The examples are given only for illustration of the technical solution of the present invention and should not be construed to limit the present invention.

Example 1

[0043] To add 0.5 mol of calcium acetate (79.9 g) into 200 g of water for dissolution completely to obtain an aqueous solution of calcium acetate. To add 1.0 mol of a free-type fish oil material (EPA34.7%, DHA 23.6%, and the total content of the free-type polyunsaturated fatty acid is 63.2%) into a reaction flask under stirring, and then heat to 40° C. Afterwards, to add the aqueous solution of calcium compound into the reaction flask, and then stir for 2.0 hours. To filter a solution after completion of the reaction, to obtain a filtered cake solid. The filtered cake solid is then dried, crushed to obtain a free-flowing fish oil polyunsaturated fatty acid-calcium product.

[0044] A filtrate by filtration is subjected to a simple distillation or vacuum distillation to obtain a small amount of available organics and wastewater. The wastewater can reach a discharge standard for directly discharge.

[0045] It may be seen by testing the polyunsaturated fatty acid-calcium fish oil product that the molar quantity of the polyunsaturated fatty acid-calcium fish oil product is 0.95 mol, the total content of polyunsaturated fatty acid-calcium is 62.9%, wherein the content of EPA is 33.9%, the content of DHA is 23.2%, the total free-type polyunsaturated fatty acid is 0.1%, the product yield is 94.5%, the product color is white, and the product quality is better.

Comparative Example 2

[0046] To add 1.0 mol of a free-type fish oil material (EPA34.7%, DHA 23.6% and the total content of the free-type polyunsaturated fatty acid 63.2%) and 0.5 mol of calcium oxide into a reaction flask under stirring, and then heat to 250° C. for 2.0 hour, to obtain a solid by cooling after completion of the reaction, and then dry and crush to obtain a fish oil polyunsaturated fatty acid-calcium product, the viscosity of the product is larger, the product color is darker.

[0047] It may be seen by testing polyunsaturated fatty acid-calcium fish oil product that the molar quantity of the polyunsaturated fatty acid-calcium fish oil product is 0.63 mol, the total content of the polyunsaturated fatty acid-calcium is 10.7%, wherein the content of EPA is 11.2%, the content of DHA is 6.1%, the total free-type polyunsaturated fatty acid is 12.3%, the product yield is 10.7%, and the product quality is poorer.

[0048] It can be seen from Example 1 of the present invention that the process obtains an aqueous solution of calcium acetate by dissolving a water-soluble calcium acetate material in water, and the aqueous solution is reacted with a free-type fish oil material at lower temperature by a mild condition to obtain a polyunsaturated fatty acid-calcium fish oil product. The process is overall simple and easy to operate, has very high reaction degree, higher yield and better product quality.

[0049] The comparative example 2 selects 250° C. as a temperature condition to obtain a polyunsaturated fatty acid-calcium fish oil product by conventional reaction of calcium oxide material. But the reaction cannot be carried out at a low temperature condition. The reaction degree is lower, because the solubility of calcium oxide is very poor. Besides the content of the polyunsaturated fatty acid-calcium fish oil product is obviously low because a larger part of the raw material or product is seriously destroyed at high temperature. So the product yield is very low, and the product quality is poor.

Examples 3-10

[0050] The objects of related parameters of Examples 3˜10 are listed in the following Table.

TABLE-US-00001 Total content of Calcium Total content of Polyunsaturated fatty acid polyunsaturated compound Water Temperature Reaction polyunsaturated fatty Yield Example material fatty acid (%) (mol/mol) (g/g) (° C.) time (Hr) acid-calcium (%) (%) 3 Methyl ester-type fish oil 98.3 Calcium acetate 5 20° C. 3 97.9 96.6 0.5 4 Ethyl ester-type fish oil 68.8 Calcium acetate 6 40° C. 3 68.2 95.5 0.6 5 Glyceride-type fish oil 47.2 Calcium chloride 2 30° C. 0.5 46.3 94.8 0.5 6 Free-type algae oil 68.5 Calcium lactate 20 50° C. 3 68.0 95.2 0.7 7 Ethyl ester-type algae oil 53.6 Calcium nitrate 1 100° C.  2 53.1 96.0 0.6 8 Free-type linoleic acid 92.7 Calcium citrate 30 30° C. 1 92.0 93.9 0.5 9 Glyceride-type linoleic 46.9 Calcium lactate 40 50° C. 3 46.2 94.8 acid 0.9 10 Free-type conjugated 13.9 Calcium chloride 4 30° C. 10 13.3 96.0 linoleic acid 0.5 11 Ethyl ester-type conjugated 27.7 Calcium fumarate 8 40° C. 3 26.8 96.2 linoleic acid 0.7 12 Free-type linolenic acid 53.8 Calcium citrate 7 80° C. 8 52.8 94.8 0.6 13 Ethyl ester-type linolenic 42.6 Calcium acetate 9 30° C. 3 41.9 95.3 acid 0.5 14 Free-type arachidonic acid 36.9 Calcium chloride 10 50° C. 7 36.2 96.2 0.5 15 Glyceride-type arachidonic 78.9 Calcium lactate 25 40° C. 2 78.1 93.4 acid 0.5 Note: the “calcium compound (mol/mol)” is referred to as the molar ratio of the calcium compound (mol) to the polyunsaturated fatty acid material (mol); the “water (g/g)” is referred to as the weight ratio of water (g) to the calcium compound material (g).

[0051] It can be seen from Examples 3˜15 of the present invention that the process obtains an aqueous solution of calcium acetate by dissolving a water-soluble calcium acetate material in water, and the aqueous solution is reacted with a free-type fish oil material at low temperature and a mild condition to obtain a polyunsaturated fatty acid-calcium fish oil product. The process is overall simple and easy to operate, has very high reaction degree, and the product yield is higher than 93.4%, and the product quality is better.

[0052] Although the present invention has been described in connection with the above embodiments, it should be understood that the present invention is not limited to such preferred embodiments and procedures set forth above. The embodiments and procedures were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention. It will be apparent to those skilled in the art that various substitution, modifications and changes may be thereto without departing from the scope and spirit of the invention. Therefore, the intention is intended to cover all alternative constructions and equivalents falling within the spirit and scope of the invention as defined only by the appended claims and equivalents thereto.