WO1998032343A1

WO1998032343A1 - Procedure for controlling hygroscopic and physiologic properties of a food salt product due to polyvalent metal halides contained therein, and product prepared according to the procedure and use thereof

Info

Publication number: WO1998032343A1
Application number: PCT/FI1998/000068
Authority: WO
Inventors: Juhani Ilpo Tapio MÄKI
Original assignee: Bergqvist, E., Eero
Priority date: 1997-01-24
Filing date: 1998-01-26
Publication date: 1998-07-30
Also published as: FI970323A0; FI970323A; AU5767698A

Abstract

The present invention concerns a procedure for controlling the hygroscopic and physiological properties of a food salt product, caused by polyvalent (valency of the cation ⊃1) metal halides contained therein. As taught by the invention, to the solution containing said halides is added material acting as ligand and which becomes linked to said halides, forming an adduct or adducts. The complexing material added is an amino acid or a derivative of such or a compound containing amino acid parts, or a mixture of such. The invention also concerns a food salt produced with the aid of the procedure, and the use thereof.

Description

PROCEDURE FO PROPERTIES OF A _ . . TU C DCT

^■0 THE PROCEDURE AND USE THEREOF

The present invention concerns a procedure as defined in the preamble to Claim 1 for controlling the hygroscopic and physiological properties of a food salt product. The invention also concerns a product prepared in accordance with the procedure, and its use.

When producing a food salt product intended to be used in various connections, e.g. in preserving foodstuffs, in other treatments thereof, in producing processed foods, in preparing food and in seasoning food, an important aim is nowadays avoidance of excessive inclusion of common salt, or sodium chloride NaCl, in the formulation of said product; the reason for such endeavours is the clearly documented harmfulness of NaCl to human health. In order that the desired effects of the food salt might be achieved all the same, endeavours are being made to replace the sodium chloride, or at least part of it, with other mineral salts, e.g. potassium, magnesium and/or calcium chloride. The cations contained in these are physiologically desirable otherwise as well. It can moreover be considered an advantage of the food salt product preparing procedure that there is in connection therewith a chance to incorporate in the product, trace substances etc. desirable in human metabolism not mentioned in the foregoing. Likewise, it is important in view of keeping the product in storage that it is substantially homogeneous with regard to its various constituents and that no detrimental grading or segrega- tion of these constituents is likely to occur during storage. This same range of physical properties also encompasses good sprin kling quality of a product meant to be used for table salt, for instance.

When in the food salt preparing process the minerals mentioned above are combined with each other and/or with sodium chloride, one has to solve in a satisfactory way the problem of hygroscopicity induced by them in the end product, either in such manner that the product displays no tendency of deliques- cence at al l or so that the product has a specific water binding capacity suited to a particular use. Another significant objective is a taste presented by the food salt product and by the food treated and/or seasoned therewith which pleases the person in- gesting the food and generally simulates the flavour of table salt.

Consideration of taste requirements as well as physiological tolerability excludes in practice the use of anions other than chloride (e.g. sulphates, carbonates and possibly some other halides).

Two patent applications have to be cited as references tangent to the field of the present invention: WO Al 93/161 17 (A 23 L 1 /237), and WO Al 92/18653 (A 23 L 1 /237).

salt from sodium and potassium chloride and a magnesium salt; with a view to counteracting the hygroscopicity of the product, the reference teaches to coat the grains of salt mixture with a non=hygroscopic substance. The second reference discloses a way to treat NaCl-K/Mg salts comprising quick drying of the dissolved mix and aiming at producing a stable double salt structure. Products according to either reference fail to meet all the requirements set as objectives for the present invention. The same is true regarding commercially available (Na)-K=Mg table salts, as examples of which the commercial products by name Seltin and lay be mentioned.

The state of art comprises Patents EP Al 59 3631 , US A 5,145,707 and US A 4,243,691 , according to which in preparing a food salt product to the starting material thereof is added a specified amino acid or equivalent. However, the starting material contains only sodium and/or potassium chloride, whereby these teachings are not encompassed by the generic definition of the present invention. As a matter of fact, the complexing of halides by action of ligand addition as taught by the invention, which constitutes the fundamental idea of the invention, cannot be realized in the case of

ϊ> v_U ι i -άi i i i i i y v_.c_. i i- ϊ il l n α v c Ucci i u iόi- iuacu , nor commercially produced. Additional calsiu supply is a highly significant nutritional factor because of osteoporosis, from which nearly all people suffer in thei r old age, and women already after thei r menopause. In certai n even extensive regions (e.g . in Japan), calci u n deficiency d ue to diet quality is indeed of pan- demic order.

Thus, we have to note that at the present time no food salt containi ng mag nesium and/or calci um is available which would meet the req uirements set i n the foregoing. The present invention abolishes this defect. The technique described in the characteristic features part of Claim 1 , that is, use of an amino acid or of a compou nd containing such to produce a complex compound with a metal salt i n which the cation is polyvalent (valency >1 ) has been considered in the following references: FSTA AN 75(12):A0660, Jou rnal of Japan Oil Chemists' Society (Yu kagaku), (1975)24 (1 ), 15-21 (Kaji- moto et al.); CA AN 105:17145, Zh. Neorg. Khim. (1985), 30(1 1 ), 2954-6 (Saleeva et al.); CA AN 117:259179, Zh. Neorg. Khim. (1992), 37(3), 683-7 (Bal kunova et al.); and CA AN 107:206125, Talanta (1987), 34(9), 817-20 (Harj u). In these referances, the chemical and spectroscopic characteristics of complex compounds produced only with g .ycine or only with leucine have been investigated, without any mention of the characteristics constituting objects of the present application. The calcium chloride adduct constituting the object of one reference (Bal kunova et al.) is intended to serve as poultry raising fodder, and therefore this too falls outside the generic demarcation of the present application.

It follows that use of glyci ne and/or amino acid derivatives towards controlling the properties of the food salt pro- duct in hand is not apparent from the state of art and that it is a novel, i nventive insight.

The aim of the i nvention is to disclose a proced u re to be used in preparing a food salt product, than ks to which the end product meets the requirements consistent with the objectives stated i n the foregoing.

The procedure of the i nvention is mai nly characterized by that which is stated i n the characteristic featu res part of Claim 1 .

As taught by the invention, the metal halides meant to be incorporated in the product are broug ht together, dissolved or i n solution in a liquid, such as water, with at least one amino acid or substance comprising amino acid parts, under such conditions

(including suitable heating) that said addition will combine with them forming a complex compound, or adduct. This is because it has been found in investigations that adducts of this kind, separated in solid form, meet well the aims which have been set for the invention.

In the simplest case, and at the same time one which is advantageous, said amino acid ligand is glyci ne, or ami noacetic acid H2 CH2COOH, or leucine. Other amino acids may also be contemplated, although with increasing carbon number solubility problems and other problems are encountered. Also usable are derivatives of amino acids, such as asparagic acid and glutamic acid, and their salts, as well as natu ral or synthetic polypep- tides, proteins, protein hydrolysates and many kinds of mixtures of the aforementioned. The compounds listed in the foregoing are, on the whole, substances associated with human metabolism, and their use in the manner disclosed by the invention, withi n certain limits, causes no physiological toleration problems. Th us, they can be used when it is desired to devise a food salt formulation with less sodium chloride than before, or with no sodium chloride at all, which may of course be incorporated if desired. When the ligand becomes lin ked with chlorides of several kinds of cations simultaneously, those aims of the invention will be realized which imply intimate combination of cations. It has especially been borne out by i nvestigations that acceptable flavour of the product, which is an aim of the invention, is excellently achieved as a rule.

According to an embodiment of the invention, the metal chloride material to be treated using the procedure is a mi neral contai ni ng sodium, potassium, magnesium and/or calcium, e.g. KC1 '

(carnallite) or a mixture of sylvi nite KCl -NaCl and MgCl2, or equivalent artificial products or mixtures.

The treatment of the i nvention may be carried out, i n order to control the properties of the product, under buffered conditions, by addi ng e.g. citric acid, malic acid or tartaric acid.

It is appropriate in ind ustrial applications of the procedure to dissolve the metal chloride components of the product to be prepared, and possibly its other components, one by one or simultaneously e.g. in water and to add the ligand component to the solution thus obtained. One may equally use, for mineral starting material, sol utions or brines from a variety of sou rces, e.g. from natural water bodies, such as the Dead See, from geo- waters of volcanic tracts, or from industry, containing the desi red mineral components in proportions which are consistent with the desired product composition or can be made consistent therewith by applying suitable treatments.

We have now found in investigations that by adduci ng one molecule, that is with equivalent ratio 1 .0 of ligand and metal chloride, good non-hygroscopicity can be achieved. By varying said ratio in limits 0.5...3.0 and by suitable selection of ligand material, it is equally possible to produce food salt having desired water binding capacity (e.g. for requirements in meat processing i ndustry), and to reg ulate the flavour of the product, for instance.

It is possible in conj unction with the procedu re of the invention, advantageously and without effort, to add either i n the process step or to the end product, other minerals, compounds and/or trace substances so that the food salt bei ng produced serves as their carrier.

The procedure of the invention is advantageous in cost since it is easy to carry out and does not requi re major production arrangements or apparatus, and since the consumption of ligand material is only determined by the quantity of material to be complexed; this consumption can be limited by means of selecting said eq uivalent ratio: investigations have revealed that equivalent ratio about 1.0 is appropriate. In an embodiment of the procedure even g reater economy is achievable by su bstituting for part of the ligand material which would otherwise be needed, e.g. colloidal silicid acid or an eq uivalent compound partici pati ng i n complex formation.

The technique of the procedu re of the invention, and results obtained i n its investigation, are more closely described with the aid of embodiment examples now following.

Example 1 In 75 ml water 20.0 g natural carnallite were dissolved, having the following composition (determined by analysis): 0.22 NaCl-0.70 KCl -MgCl₂-6 H₂0; this starting material was characteristically a large-crystalline, colourless crystal mass, and it began immediately to deliq uesce u nder influence of air humidity. The minimal quantity of unsolved material was removed by filtration. To the solution was added, with agitation and heati ng, L- glycine in quantity equivalent, relative to MgC^, 5.25 g (0.07 mol), thereafter raisi ng the temperatu re of the sol ution to 70° C and inspissating the solution. Yield was 23.2 g of crystalli ne, white product with neutral flavour, in normal conditions completely stable, i.e. not hygroscopic at all.

The product of Example 1 is well suited to be used as a constituent of a food salt preparation, for instance on the side of potassium chloride and, possibly, sodi um chloride, desirability of both latter constituents being determi ned by physiological aspects. Substitution of racemic glycine for the L-glycine used i n Example 1 produced equal result.

Example 2

In 100 ml water were dissolved 20.0 g natural carnallite as used in Example 1 and 6.0 g natural sylvinite having composition 0.55 KCl -NaCl. After filtration of the solution, 6.25 g (0.07 mol) L-alani ne were added. The sol ution was heated to 70° C and inspissated. 24.3 g of crystalli ne, white, slig htly sweet, i n normal conditions stable salt product were obtained. This product crystallized somewhat less rapidly than the salt prepared i n Example 1 .

The salt of Example 2 is suitable, as such, to be used for food salt; owi ng to complete natural provenance of the start- ing materials, it has higher trace substance content than the salt product of Example 1.

Example 3 A test was carried out as in Example 2, except that, instead of alanine, 9.31 g (0.07 mol) asparagic acid were added. Yield: 27.2 g of crystalline, white salt product with somewhat acid flavour, stable in

The salt product of this example has proved well suit- for seasoning e.g. fish dishes, either as such or mixed e.g. ιalt of Example 1.

t-Λ niμic *τ

To the starting material solution of Example 1 was furthermore added, calcium chloride CaC^ in the form of dihydrate, the amount added being 5% of the magnesium chloride

.y^o y (0.0035 mol) glutamic peri εnt was continued as in Example 1. The resulting salt product, amounting to 24.5 g, was crystalline, white, and had a slightly acid flavour, somewhat resemblant of meat. It met the requirements set as to stability.

In this example, stabilization of physiologically useful and desirable calcium chloride, known to be enormously hygroscopic, was entirely succesful.

For this example an amino acid mix was prepared, simulating the amino acid composition of cereal protein, according to following formulation: Amino acid Quantity, Quantity, g mol alanine 4.3 0.0483 arginine 7.6 0.0436 asparagic acid 12.2 0.0872 cysteine 1 .3 0.0107 glutamic acid 10.1 0.1298 glycine 4.2 0.0559 histidine 2.6 0.0168 isoleucine 4.9 0.0373 lycine 8.2 0.0625 methionine 1 .3 0.0087 phenylalanine 5.2 0.0315 proline 5.1 0.0443 serine 5.2 0.0495 threonine 3.8 0.0320 tryptophan 1 .3 0.0064 thyrosine 3.8 0.0210 valine 5.0 0.0427

This mix was moistened, dried and ground in order to ensure homogeneity; its calculated equivalency was 0.00765 eq/g.

The experiment of Example 2 was repeated, using now instead of alanine, the quantity equivalent in relation to MgC^ (9.15 g; 0.07 eq) of above amino acid mix. When the solution was cautiously inspissated, aiding with microwave heating, which promoted crystallisation, the result was 27.3 g of crystalline, pleasant flavoured salt preparation, which was stable in normal conditions.

The product of this example is advantageous in use as starting material for herbal and spiced salt preparations.

Example 6

The same chloride solution as in Example 5 was used in this experiment, that is 6.0 g sylvinite and 20.0 g carnallite in 100 ml water, to which in this instance the same amino acid mix was added as in Example 5, at half the quantity, that is 4.58 g (0.035 eq), and 1.0 ml of 15% colloidal silicic acid. The solution was cautiously inspissated, using microwave heating, whereby 22.7 g of crystalline, white salt product with pleasant flavour was obtained, which was stable in normal conditions. Redissolving- this product in water produced a clear solution.

The clearness of the solution resulting from redissolv- ing indicates that the silicic acid participated i n complex forming.

The embodiment of this example is advantageous when there is a desire to mi nimize the costs accruing from amino acid consumption. A process according to this embodiment also enables the quantity of trace substances present in the salt preparation to be artificially elevated if desired.

Example 7 In 100 ml water were dissolved, li ke in Example 2,

20.0 g carnallite and 6.0 g sylvinite, these having the composition stated in that example. To the solution were added, with mixing, 5.0 g protein hydrolysate and 1.0 ml 15% colloidal silicic acid. The mixture was homogenized and spray-dried, whereby there was obtained 25.0 g of slightly yellowish salt product with agreeable flavour. By way of trial, herbal salt was prepared from this product by adding 10% dried and g round herbs; this herbal salt displayed satisfactory stability in normal conditions.

Example 8

A test equivalent to Example 1 was made in which however to the carnallite solution (75 g) were added, instead of L- glycine, 4.64 g (0.035 mol) N-glycylglycine and 1 .0 mol 15% silicic acid. On inspissation of this solution 22.8 g of white, crystalline salt product were obtained, which was stable in normal condition.

The product prepared in this manner can be used for starting material of food salt preparations. The test j ust described illustrates the effect of dipeptides in the procedure of the i nvention on product hygroscopicity.

In the foregoing the invention has been primarily described with the aid of embodiment examples. It is obvious to a person skilled in the art that various embodiments and applica- tions may vary within the scope of the i nventive idea expressed by the claims followi ng below.

Claims

1. A procedure for controlling the hygroscopic prop- erties and/or physiological properties, such as flavour, of a food salt product, caused by a polyvalent (valency >1 ) metal halide, or halides, contained therein, e.g. magnesium and/or calcium chloride, characterized in that to the starting material containing said halide or halides dissolved in water, is added ligand material con- taining atleast one amino acid or amino acid derivative or amino acid parts; the mixture thus obtained is heated to about 70┬░C for complexing the added material with said halide or halides, possibly together with other components of the mixture, such as e.g. potassium and/or sodium chloride; and the resulting material is sep- arated in solid form if desired, e.g. by crystallizing or inspissating, or is used in solution form towards nutritive ends.

2. Procedure according to Claim 1 , characterized in that the complexing material added is glycine or leucine.

3. Procedure according to Claim 1 , characterized in that the complexing material added is asparagic acid or glutamic acid or a salt of such.

4. Procedure according to Claim 1, characterized in that the complexing material added is a dipeptide.

5. Procedure according to Claim 1 , characterized in that the material added is a protein, such as cereal protein, or a protein decomposition product, such as a hydrolysate of such.

6. Procedure according to any one of the preceding claims, characterized in that the equivalent ratio of the quantity of material added to the quantity of metal halide is in the range of 0.5...3.0, advantageously within 1.0...2.0, and most advantageously about 1.0.

7. Procedure according to any one of the preceding claims, characterized in that a silicon compound, such as colloidal silicic acid, is used to replace part of the material containing amino acid which is added.

8. Procedure according to any one of the preceding claims, characterized in that in the product being prepared are incorporated, either in the processing step or thereafter, desired other minerals, compounds and/or trace substances or equivalent.

9. Procedure according to any one of the preceding claims, characterized in that acidity regulating substance is add= ed, such as citric acid, malic acid, tartaric acid or a derivative of these.

10 A food salt produced with the aid of a procedure according to any one of the preceding claims.

11. The use of a food salt according to Claim 10 in the preparation or preservation or other treatment of a foodstuff or nutritional product, such as a semi-finished food product, prepared food product or food portion.