United States Patent 0 rice

3,809,773
Patented May 7., 1974

lighter in color but much less stable. Iron rapidly comes

out of these ferrous sulfate solutions in the form of an

3,809,773

insoluble red precipitate.

An object of this invention is the provision of a highly
stable preferably lightly colored iron solution in a form

METHOD FOR PREPARING A LIQUID IRON

FORTIFYING COMPOSITION
George N. Bookwalter, Peoria, Ill., assignor to the United
States of America as represented by the Secretary of

convenient for addition to a variety of food products.

In accordance with the above objects, I have discovered

Agriculture

No Drawing. Filed Feb. 25, 1972, Ser. No. 229,581

a method of preparing highly stable liquid iron-fortifying

compositions which comprises ?rst preparing aseptic aque

Int. Cl. A231 1/30

U.S. CL 426-380

4 Claims

IO ous solutions of ferrous or ferric salts and completely

blending the resulting solution with a high conversion

ABSTRACT OF THE DISCLOSURE

- A method for preparing highly stable, liquid, iron
fortifying compositions containing up to 1 percent by
weight of ferrous or ferric ions. An aseptic and deaerated 15
aqueous solution of an iron salt is prepared and blended
with a high D.E. corn syrup. Food products such as baby

formulas, bread and fruit drinks may be iron-supple

mented with the iron-fortifying compositions.

A nonexclusive, irrevocable, royalty-free license in the

invention herein described, throughout the world for all

corn syrup optionally containing up to 40 percent sucrose

based on total weight of solids under aseptic conditions.
The ferrous or ferric salts, syrup, and water are blended

in proportions such that the resulting compositions con

tain up to about 1 percent by weight ferrous or ferric ions,
from about 70 percent to about 80 percent by weight total

solids, the remainder being water. Stability is defined herein

as being able to withstand ordinary storage and use condi
20 tions without loss of dissolved iron and without occurrence

of fermentative reactions (i.e., biological stability).

Compositions prepared according to the above method

have the advantage of being in an easy-to-use liquid form

which lends itself to automation. High conversion corn
to grant sublicenses for such'purposes, is hereby granted 25 syrups or their equivalents are essential ingredients in a
wide variety of food preparations including baked goods,
to the Government of the United States of America.
purposes of the United States Government, with the power

_ BACKGROUND OF THE INVENTION

confections, beverages, jams, jellies, and fountain syrups.

However, iron salts are normally di?icult to dissolve in

This invention relates to the preparation of stable liquid
syrups, and in mixing large batches it is very di?icult to
iron compositions which can be used to increase the iron 30 determine when the salts are completely dissolved. The

content of food products.

' The Food and Nutrition Board of the National Academy

of Science has set the recommended dietary allowance of

iron at 18 mg. per day--an amount so great that it can

not beisupplied by existing foods without increased iron

forti?cation. For instance, in bread the present standards
require 13.0 to 16.5 mg. iron per pound of flour, and it
has been proposed by the baking industry that this should
be increased to 50 to 60 mg. iron per pound of ?our

(Federal Register, Apr. 1, 1970). The Commissioner of

the Food and Drug Administration has proposed 40 mg.
iron per pound of ?our (Dec. 3, 1971).
'
'
Among the best sources if iron for food uses are salts

such as ferrous sulfate, ferric ammonium citrate, ferrous

instant method provides quick mixing and assurance of

complete solution.
When the liquid iron-fortifying composition contains
ferrous sulfate heptahydrate as the iron-fortifying agent,
it has the further advantage of being substantially color
less. This is a great advantage in certain food products
such as baked goods where off colors are objectionable to
consumers.

DETAILED DESCRIPTION OF THE INVENTION

Iron salts useful in preparing liquid iron-fortifying com
positions must be water-soluble and nontoxic at addition
levels described herein and include ferric ammonium
citrate, ferric choline citrate, ferrous gluconate, and fer

fu'marate, ferric choline citrate, and ferrous gluconate. 45 rous sulfate. Any iron salt within the above limits will be
considered equivalent for the purpose of the invention. Fer
Commercial preparations of these compounds include the
rous sulfate heptahydrate (FeSO4-7H2O) is preferred
relatively insoluble -. FeSOy 1.2H2O (32.1 percent Fe).
primarily because it provides compositions which range
When the ferrous sulfate compound is combined with
from colorless (compositions containing up to 0.1 percent
wheat flour, 01f ?avors develop during storage. Therefore,
it is usually added during the baking process at the dough 50 ferrous ions) to very slightly blue (compositions contain
ing 0.1 to 1.0 percent ferrous ions) while other ferrous or
mixing stage in tablet form. The tablets, added at the rate
ferric salts produce compositions which range from medi
of one per 100 pounds of ?our, are broken up by hand
which causes some doubt as to the completeness of distri

um to dark amber. These amber colors are easily de

tected in food products which are not themselves highly

bution. This method is not easily adaptable to automation.
For baking and other food processing, a liquid-iron 55 colored.
Ferrous sulfate is preferred also because it is the least
composition would have great advantages. However, pres
expensive source of iron for physiological purposes.
ent commercial liquid preparations are not particularly
High conversion corn syrup is de?ned herein as a syrup
suitable for food uses. One, for example (US. 2,822,317),
made by the partial acid hydrolysis of corn starch and
combines a nontoxic ferrous salt with a polyhydric alco
hol, l-ascorbic acid, and sometimes ethyl alcohol to main 60 having a dextrose equivalent (DE) of from about 60 to
tain the iron salt in an aqueous solution. These relatively

expensive compositions are pharmaceutical preparations

about 68 and a solids content of about 80 percent by

'weight (The Encyclopedia of Chemical Technology,

Kirk and Ottman editors, 2nd edition, vol 6, pp. 926~932).

for treating hypochromic anemias and are not intended for
An extra high conversion corn syrup having a DE of 70
general food use. They are usually a dark amber color
which indicates that part of the soluble iron has reacted 65 was also used to prepare the instant compositions and is
considered for the purpose of this invention equivalent to
with dissociated hydroxy ions from the water. The solu
the high conversion syrup described above.
tions must be stored in dark amber bottles in a cool place

to prevent further degradation.

Simply mixing together the desired amounts of iron

salts, high conversion corn syrup, and water does not pro
Water solutions of iron salts such as ferric ammonium
citrate, ferric choline citrate, or ferrous gluconate are 70 duce a stable liquid iron-forti?ed composition. Prepared
in this manner, compositions quickly darken due to pre
fairly stable but are quite highly colored. Water solutions
cipitated iron. However, iron will not precipitate when pre
of ferrous sulfate, on the other hand, are substantially

3,809,773

pared according to the following procedure. All the proc

transferred after preparation, preferably at a temperature

ess steps and storage should be conducted under aseptic

of at least 180 to 200:F.into'sterilizedco'n?tiners'in
conditions to insure biological stability of the products.
the laboratory these containers consisted of clear glass
The preferred manner of achieving this stability is de
pint bottles which were tightly screw-capped and inverted.
scribed for each step. However, those skilled in the art 5
Compositions containing ferrous sulfate are colorless
will be aware of many other equivalent methods.
even when the most concentrated ferrous sulfate solutions
The ?rst step of the process is the preparation of an
were used. The slightly blue color'of the ~iron solutions is
aqueous solution of ferrous or ferric salts. It is preferred
not detected in the ?nal product. All ?nal'products arp
that the water be boiled before dissolving the iron salts
stable during storage and in food' processing at tempera
to provide an aseptic solution. When ferrous salts are 10 tures of 0 to 100 F. in darkness or direct sunlight?'lihey
used, boiled deaerated water cooled to about 70 to 90
may be frozen for extendediperiods of time withoriii loss

F. eliminates clouding of the resulting solution, prob

of stability or functional properties. ~Good ?avors, physi

ably caused by oxidation of the ferrous ion. Clear solutions

containing up to 26 percent by weight FeSO4~7H20 can

cal-stabilities, and biological stabilitiesewere maintained

of iron' and water desired in the ?nal composition. Final

compositions containing more than 30' percent water by
weight tend to be biologically unstable, and at this water

nonformulated high conversion cor'n' s'yrup', but "fof all

purposes for which these compositions are intended they

after storage for 1 year at room temperature. A slight

be prepared in this manner. The concentration of iron in 15 yellowing occurred tothe same extent iln_.both the instant
these solutions is varied in accordance with the amounts
compositions containing ferrous sulfate and samples of

considered
following
to embodiments
be essentially colorless.
are intended
'? to further-de
' " ' L
content'any dissolved ferrous or ferric ions over about 1 20 areThe
scribe the invention which is de?ned only by the claims." _
precipitate. The concentration of ferrous or ferric ions
EXAMPLES 1-4
in the examples has been calculated from the total amount

percent by weight of the ?nal composition will tend to

of iron salt in solution. It is possible that all dissolved iron

Aqueous iron solutions were prepared by mechanically

is not in free ionic form, but could be bound in some 25 mixing for about 10 minutes a ferrous or ferric [salt indis
manner to the anion or to other compounds present in
tilled water which had previously boiled (to deaeratenand

make aseptic) and cooled to between 70 and 90 E'At

the composition. However, this is not important for nutri
this point a mineral acid was added to some of the solu
tional purposes. Concentrations of iron described herein
tions to lower the pH of the ?nal composition.
7
_
in terms of weight percent of ferrous or ferric ions will
The iron solutions were then added by means of a fun
be understood to include all iron contained in the added 30
salt.
nel having its exit end protruding beneath the surface of
the liquid to a syrup which had been previously heated to
A small amount of acid can be added, preferably to the
between 180 and 200 F. During the addition and .for
aqueous iron solution, to bring the acidity of the ?nal
about 10 to 30 seconds after all the iron solution had been
composition down to about pH 2. In some cases where the
composition is used or stored under drastic conditions, 35 added, the syrups were mechanically stirred to insure

complete mixing. The compositions, still at a temperature

decreased. Adjusting the pH downward to about 2 will
of 180 to 200, were transferred to clear glass pint bottles
which were then screw-capped and inverted to eliminate
maintain stability. Without addition of acid a composi
fermentation during storage.
I
tion containing 1 percent ferrous ions will have a pH of
40
about 3.5.
Amounts and kinds of starting materials and ?nal prod
ucts for several composition preparations are described-in
After the aqueous iron solution has been prepared, it
Table l.
should immediately be mixed with the syrup. Immediately
is de?ned herein as the length of time before the occurrence
of clouding of the iron solution. This can be as long as 1
TABLE 1 '
hour. The preferred temperature range for the syrup 45
Examples
during the mixing step is from about 65 to about 300

such as high temperatures (e.g., 120 F.), stability is

F. Viscosity noticeably increases at temperatures below

65 F., and the syrup begins to discolor at temperatures -

of about 300 F. To maintain aseptic conditions, it is pre

ferred that the syrup to which the iron solution is added be 50
at a temperature of from about 180 to about 200 F.
The syrup can be all high conversion corn syrup or it
can contain up to 40 percent sucrose, based on total solids
weight. Sucrose solutions can be prepared which have up
to 67 percent solids and 33 percent water. When ferrous 55
sulfate is dissolved in this solution, a black precipitate

forms which changes to red on standing. A similar precipi

tate forms when ferrous sulfate is dissolved in high con
version corn syrup containing less than 70 percent solids.
It is, therefore, believed that the precipitation of the fer
rous salts which occurs in blends containing less than 70
percent solids is due to excessive amounts of water. Stable
liquid iron-forti?ed compositions can be prepared accord
ing to the invention that contain 70 percent by weight
solids consisting of 40 percent sucrose and 60 percent high
conversion corn syrup solids, and that also contain up to
1 percent ferrous ions. Dextrose can also be added in the
same manner as sucrose but in smaller amounts since the

maximum amount of solids in a dextrose solution is only

50 percent by weight. While the lower limit of solids con

tent in the liquid iron-forti?ed composition is preferably

70 percent by weight, stable compositions can be pre

82% solids by weight ........... -- 3, 619

Starting material g.:

High conv

on corn syrup DE 65,

Sucrose___________________________ _.

FeSOr 7HO solution

liltiira'aerr'

3,570

3, 938

524

523

3 5
100

164.5
400

230
380

207
360

Total solids content, wt. percent.... 75.5

Ferrous ion, wt. percent 1
0.015

74.9
0. 69

Water, wt. percent___

Remainder

................... --

Final composition:

pH

3,938

'3

75. 4
1. 01

75. 1
0. 92

' .

5. 0

20

3. 6

2. 3

I Calculated from total amount of iron salt added.

All compositions were colorless and were. stable at least

1 year at room temperature (70 F.). At storage tempera

tures of 120 F., Examples l-3 showed a tendency to dis
color indicating some unstability. Example 4, on the other

hand, showed complete stability at that temperature.

EXAMPLE 5
An iron-fortifying composition was prepared as in Ex~

ample l-4 with 3690 g. of regular corn'syrup (DE 42,

82 percent by weight solids), 524 g. sucrose, 3'41v g. water,
and a ferric ammonium citrate solution1containin'g'4.l g.

iron salt and 100 g. deaerated distilled water. The product

pared which contain as high as 80 percent by weight solids.
was amber in color, contained 0.015 percen'tby weight
To insure a ?nal composition that maintains biological
ferric ion, 76.4 percent by weight total solids, and had a
stability under storage and use conditions, it should be 75 pH of 5.8.
' I
'

3,809,773

5
EXAMPLE 6

(The sponge formula was fermented 41/2 hours and the

ingredients of the dough formula were incorporated.)

An iron-fortifying composition was prepared as in Ex

The dough properties, ?avor, color, and general bak

ing characteristics of the bread containing liquid iron
,fortifying composition (72 mg. Fe/pound ?our). were

amples 1-4 with 3690 g. of regular corn syrup (DE 42,

82 percent by weight solids), 524 g. sucrose, 341 g. water,
and a ferric choline citrate solution containingi518 g.
iron salt and 100 g. deaerated distilled water. The product
was dark amber in color; contained 0.015 percent by

similar to bread containing the the more cumbersome

dried FeSO4-1.2H2O and to unforti'?ed bread. Present
standards require 13.0 to 16.5 mg. Fe/pound ?our and
proposals of up to 60 mg. Fe/pound ?our have been made.

weight ferric ion, 76.2 percent by-weight totalgsolids, and

had a pH of 5.0.

'

10
EXAMPLES 7-10
The following four compositions were prepared as in

Liquid iron-fortifying composition of Example 3 was

utilized in the iron forti?cation of an orange-pineapple
drink. The formulation was as follows:

Examples 1-4 with a DE 70 corn syrup as shown in

Table 2.
TABLE 2

Examples
7

Orange-pineapple drink:
9

10

Starting material, g.;

Extra high conversion corn syrup

DE 70, 82% solids by weight.-. _- 3,600
Sucrose ........................... -_

522

3, 100

4, 000

850

4, 000 20
0

Salt .......................... ..

206

201

194

202

Deserated distilled water .... .-

380

880

386

380

Remainder

Final eomposit on:

Total solids content, wt. percent..Ferrous ion, wt. percent 1.. -

75

75

75

0.85

0.85

0.85

Water, wt. percent ......... -.

pH

8. 2

72 25

0. 85

Remainder

3.2

3.3

G.

High conversion corn syrup __________ _..

123

Sugar

328

Sodium citrate ______________________ _.Citric acid _________________________ .._

Water

FeSO4-7HzO solution:
Water.i ______________________ __

EXAMPLE 13

3. 2

1 See footnote 1, Table 1.

4.7
4.7

2,515

Orange juice (reconstituted) __________ _Pineapple juice _______________ -_u..____

268
105

Orange oil

Tween 60 '

_____________ .._- __________ _..

'

0.5
0.5

McCormick F.D.&C. red color (liquid) _---

0.4

McCormick F.D.&C. yellow color (liquid) ._

0.2

Liquid iron forti?cation composition (from

30

EXAMPLE 11

Example 3) (4.4 m1.) ______________ ..-

Total

Liquid iron-fortifying composition of Example 1 was

6.2

3,356.2

utilized in the iron forti?cation of an infant baby formula.

The baby formula prepared was as follows:
Carnation evaporated milk ______________ _..

The forti?ed orange-pineapple drink (10 mg. Fe/

quart) was prepared by combining all ingredients except
G. 3'5 the liquid iron forti?cation composition and heating to
200 F. The iron preparation was poured in, blended, and
282

Water

370

Baby formula:

the bottles were ?lled and capped at 190 F. Comparisons

revealed no ?avor or color differences between orange~

Liquid iron forti?cation composition (from

2 40 pineapple drink with or without iron.

Example 1) (30 ml.) ________________ _-

'

I claim:

1. A method of preparing highly stable, liquid, iron

Total
694
fortifying compositions which comprises ?rst preparing
The iron preparation was blended with water which
aseptic aqueous solutions of ferrous or ferric salts, and
had been heated to 125 F. and then blended with the
completely blending the resulting solution with a high
evaporated milk. The mixture was added to baby bottles 45 conversion corn syrup optionally containing up to 40
which were placed in a sterilizer and cooked for 25
percent sucrose, based on total weight of solids, under
minutes along with identically prepared unforti?ed baby
aseptic conditions, said ferrous or ferric salts, syrup, and
formula. The bottles were cooled and stored in a
Water being blended in proportions such that the resulting
refrigerator as would be done in usual practice. Appear
compositions contain up to about 1 percent by weight
ance, ?avor, and iron content (2.2 mg. Fe/bottle) were 50 ferrous or ferric ions, from about 70 percent to about 80
superior to the unforti?ed baby formula.
percent by weight total solids, the remainder being water.
2. The method of claim 1 in which the ferric salt is
EXAMPLE 12
ferric ammonium citrate.
Liquid iron-fortifying composition of Example 2 was
3. The method of claim 1 in which the ferric salt is
utilized in the iron forti?cation of sponge-dough bread. 55 ferric choline citrate.
The procedure followed standard baking practice. The
4. The method of claim 1 in which the ferrous salt is
bread formulation was as follows:
ferrous sulfate heptahydrate and is ?rst dissolved in
aseptic, deacrated water at from about 70 to about 90
Breadzsponge formula:
G.
F. immediatelyafter which the resulting solution is com

Wheat ?our ________________________ __

420

Water

268

Yeast, compressed ___________________ _..

Yeast food _________________________ _.-

14

total weight of solids, under aseptic conditions, the re

sulting composition having a pH of from 2 to 5.

3.5

Dough formula
Wheat ?our ________________________ _..
Water _.-

pletely blended with a high conversion corn syrup

optionally containing up to 40 percent sucrose, based on

65

Liquid iron forti?cation composition (from

Example 2) (11.5 ml.) ____________ __

16.2

Salt _-Dextrose hydrate ____________________ __

14
28.7

Nonfat dry milk _____________________ __

Vegetable shortening ________________ __

References Cited
UNITED STATES PATENTS

280
174

70

21
21

Total ____________________________ __ 1,260.4

75

2,985,559

5/1961

Coles _-....________ __- 424-295

3,692,542
3,668,007
2,822,317
3,344,027
2,939,820

9/ 1972
6/1972
2/ 1958
9/ 1967
6/1960

Walon ____________ -_ 99142

Eggcr et al _________ _.. 99142
Gulesich et a]. .... _.. 424-147
Hughes __________ _.- 424295
Gerber et al _______ _- 424295

(Other references on following page)

3,809,773

UNITED STATES PATENTS

>
3,607,310 9/1971 can. ____________ __"_ 99__1'1

Remington's Phnrmaceuticalsciences, 13th ed., 1965,

pp. 902-905 (Copy available Chem. Lab. US. Pat. 01f).

233???? 33773 if???531311111353?

MORRIS 0- .WOLK, 'Primary Examiner-

2,820,740

1/1958

London et a1 ______ _'__ 424-147 5 S. MARANTZ, Assistant Examiner

3,734,742

5/1973

Morse et a]. ________ __ 9928

~
OTHER REFERENCES

'

'

US. Cl. X.R.

.

National Academy of Sciences, Chem. Used In 'Food

Processing, 1965, p. 58 (Copy available Gr. 170 US.
Pat. 01f).

"

127*29 424'447 295; 426_213 218

'