Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
13~501~
. . :
~
,. ''',
BACKGROUND OF THE DISCLOSURE
. : ,
This invention relates to an improvement in the process
of making l l zinc and l l manganese complexes with alpha
amino acid~, part~cularly methionine In that ense, it
represents an improvement over the proce~ses disclosed in
commonly owned United States Letters Patents 3,941,818
issued March 2, 1976, entitled ~l~l ZINC METHIONINE COMPLEXES"
and United State~ Letters Patent 3,950,372 issued April 13,
1976, and entitled ~1 1 MANGANESE ALPHA AMINO ACID CC~IPLEXESn. :
Both of the previously issued patents relate to the 1 1
complexed 8alt8 per e, and to general proc-sses for
preparing the same The novel s~lt~ have a8 expres~e~ in
the earller issued patents, the u-eful --ture~of being
highly body absorbable nutritional uppl-ments for both
1~ animals and humans to provide readlly avail~ble sources of
zinc ions on the one hand, and mang-ne-e ions on the other
hand
In the commercial preparation of the~e l l metal amino
acid complexes, there have been from~t~ime~to time certain
problems in solubilizing the precursor sa1ts and the alpha
amino acid, both of which exist ln solid powdered form As
a result, even though the salts are theoretically highly
soluble in water, the amount of necessary mixing to assure
substantial dissolving teven at elevated temperatures) in
order to provide the necessary intimate contact for adequate
reae~ing between the two to form l l complexes of~ the zinc
~nd/or manganese and the alpha amino;acid is quite excessive
¦ Thus, there has been an inherent problem in the preparation
I ~ :,
~' ~
1325014
1 technique, both from the standpoint of the very practical
problem of adequate dissolving even in hot water, and also
the problem of assuring that the product i8 subQtantially
all the desired 1:1 complexes.
Accordingly, there has been ~ roal and a continuing need -~
for the di~covery of proce3s improvement~ which allow~ the
ready dissolving of ~he in~t~al precur~or reactants or
ingredients, and which wlll simultaneously assur- product
yield in high amounts of the de~irod 1:1 complexes of the
metal ions and the alpha amino salts.
This invention hDs as it~ primary objective the fulfillment
of this need ln order that the 1:1 manganese alpha amino
acid complexes of United St-to~ Letter- Patent 3,950,372 and
the 1:1 zinc alpha amino acid complexe~ of United States
Letters Patent 3,941,818, may be prep~red ea8ily without
long process delays and in high yield of the desired 1:1
complexes.
For details of desirability and utility of l:l manganese
alpha amino acid complexe~, see the previously referred to
U.S Patent 3,950,372 which is incorporated hereln by
reference. For details of desirability and utility of 1:1
~inc alpha amino acid complexes, see United States Letters
Patent 3,941,818 which is incorporated herein by reference.
The method of accomplish~ng each of the objectives of -
~5 I this nvention will become apparent from the detailed
decription of the invention which follows hereinafter.
SU~1MARY OF THE INVENTION
l This invention relates to a process improvement which
3~ 1~ -3-
1 32501 4
1 ~ llo~ increased eAae Df pr-paratlon in high ~lelds of 1
¦ c plexes of zinc and mnngane3e wlth ~lpha amino acida to ¦
provide in high yield the desired 1:1 complexes in a form
which can be readily absorbed biochemically after ingestion
by animals and humans to provido adequate and proper dietary
levels of zinc ~nd methionine as necessary for proper
health, weight gain and dietary balance. The reaction is a
straightforward reaction between the respective zinc salt
and the respective manganess ~alt and the alpha amino acid,
which are both at least partially di~solved in water. It is
significantly catalyzed, both from~the standpointof solùb~lD7rlsn
of the respective salts and from the standpoint of producing
the desired 1:1 complexes between the re~pective zinc ion
and manganese ion and the desired alpha amino acid, preferably
methionine, by conducting the reactlon in the presence of
catalytically effective amount of ferric ~on, preferably in
the form of ferric ~ulfate. -~
. - ~ , ~ . ':'.
DETAILED DESC~IPTION OF T~lE INVE~lTION
It is important to note that the respective zinc and
manganess compounds which are prepared in accordance with
this in~ention are referred to as complexed salts. These
salts are to be carefully distinguished from conventional
salts such as~ for example, zinc chloride or manganese
chloride. 5uch conventional salts such as zinc chloride or
manganes~ chloride contain only an electrostatic attraction ¦~
between th~ cation and the anion. The 1:1 complexed salts
prepared by this invention differ from conventional salts in --~
~hat while they have an electrostatic attraction bstween the
-f ~1 -4-
ll ,,"
1325014
~ .'.'
1 1 c ion and the ~nion, there io also a coordinltion bond between ~
the cation and the amino moiety of the alpha amino acid. -
The preferred alpha amino acid for use in this invention
is methionine. From the ~tandpoint of both zinc complex
salts and the manganese complex 8alt8, however, it should be
understood that other alpha amino acids may be employed as
well. Preferably those are es ential alpha amino acids.
Those essenti~l alpha amino acids which are preferred for
utilization in forming the 1:1 complex salts of this invention
are arginine, hi~tidine, isoleucine, leucine, lysine,
methionîne, phenyl~lanine, threonine, tryptophane, and
valine. Glycine, while not an essential amino cid, is also
a preferred alpha amino acid in that it is readily available --
and can be utilized for synthesi~ of the complex salts of
this invention. The two mo~t pref-rred natural alpha amino
acids are methionine and glycine.
With regard to the preferred zinc methionine complexed
salts which are prepared in accordance with the improved
process of this invention, they have~the general Eormula:
20 ~ ~ ++
~CH3-S-CH2-CH2-CH-~-OZn lwX ~;
wherein X is an anion and w is an integer equal to the
anion-c charge of X. The cation of these complexed salts is
represented by the bracketed material in the above formula
and represents a 1:1 complex of zinc and methionlne.
Wi~h regard to the manganess alpha amino acid complex
salts of ~he present invention, they have the formula:
I LR C ~ O Mn ++~ X
3 0 ¦ N112 W
l -5-
~, .
1 3250 1 4 ~: :
1 wherein R i5 an alpha moiety of alpha amino acid, preferably
methionine or glycine, X is an anion, and W is an integer
equal to the anion charge of X The cat$on of these complexed
salts i8 represented by the bracketed material in the above
formula and represents a 1:1 complex of manganese and alpha
amino acid
The proces of preparing the deslr-d zlnc and methionine
1 1 complex salts of the alpha amino aclds~referred to
herein, in each instance as the~ -arlier p-tent- mention, ls
straightforward and direct Co _ only lt~begin- wlth the use
of a water soluble zinc salt and/or o w-ter~-oluble manganese
salt, respectively Sultable zlnc solt~ ~hioh c~n be ~-
employed are the halides, the sulfates, and the~phosphate6
The desired weight ratio of zinc alt~to methionine is ~
within the range of 1:1 to 2sl, pref-rably 3 2. ~Suitable
manganese salts which con be mployed are llkewise halides,
sulfates and phosphates. The deslr-d w-ight ratlo of manganese -~
to methionine is 1 1 to 2 1, preferably~4:3 In~each ~
instance, the sulfate salts are~preferr-d from~tbe standpoint
of availability and, at least currently-, oost
In the general proce~s, these~salts are at least partially
water dissolved, preferably at elevated temp-ratures
Temperatures within the range of from~abQut 180F~ to about ~-
205~ have been found desirable,;most preferably temperatures
with the range of 190F to about 205F In actu~al practice,
one common tec~nique is to stlr the salt into a water
solution while simultaneously injecting steam to elevate the
temperature within the desired range
In the most preferred embodiment of the present invention
~0 . '
-6-
1325014
1 the catalytic ferric ion is next added. It should be under-
stood, however, that the catalytic amount of ferric ion can
be added both before the addition of the alpha amino acid or
after, with before belng modestly preferred.
As previously m~ntioned, it ha~ been di~covered that
when the react$on between the water soluble metal salt and
the alpha amino acid ~s conductsd in the pre~ence of R
catalytically effective amount of ferric ion, two desirable
things occur. In the first in3tance, the dissolving of the
salt and the amino acid in the water appears to be significantly
enhanced from the standpoint of rapidity and in the second
instance, there i5 an increased yield of the desirabl4 1:1
complexes formed. _
It is not known prscisely why the ferric ion catalyzes
the process, but it nevertheles~ does~ The ferric ion may
be added in the form of any water soluble salt such as
ferric chloride, ferric sulfate, ferric phosphate, ferric
acetate or any other suitable water ~oluble ferri~c salt.
~he most preferred are ferric chloride and ferric sulfate.
The amount added can be from about 2% to about 10% based
upon the dry weight of alpha amino acid, preferably from
about 4% to about 8~ based upon the dry weight of alpha
amino acid employed. For the most preferred alpha amino acid
o~ this invention, methionine, 4% by weight has been ~ound
best in experimentation to date. However, it should be
understood that any amount within the range from about 2~ up
to about 10% by weight of the alpha amino acid will work.
¦ The lower limit expressed herein, i.e., 2~, is about the
3~ ¦ ~inimum quantity needed for any sign~ficant improvement.
I -7-
_~... I
I 1 32501 4
1 ~he upper level is a practical and economic level, since
amounts in excess do not ~eem to add anything except expense.
After the preferred c~talyti~ amount of ferric ion i5 added
to the water ~oluble salt of either zinc or manganese, and
S mixed therein, the desired alpha amino acid fs then stirred
into the reaction mixture ~long with increa~ed injection of
steam in order to elevate the temper~ture again to within
the desired temperature range.
It is noted in the rcaction proc-~3 that where the
ferric ion i8 used, almost immed~ately the solution becomes
clear, lumping does not occur-, and in the c~e of zinc
methionine complexes, it immediately turns to a clear
reddi h brown ~olution. In the c~se of manganese methionine
complexes, the reaction immediately turns to a d~istinct
clear ~olution of similar color. In both instances, there is
no problem of "lumping~ and the re~ction becomes straightforward ;
and direct to the desired lsl complexe .
~fter the re~ction i~ completed, which i8 ordinarily a
~atter of minutes, but may be up to an hour or longer if
desired, the product is ready for fini~hing.
If product concentrate is d-sired, it may be spray dried -
in each instance. On the other hand, if the product is to be -
mixed with a carrier, such as a cereal product, it may be
mixed together at varying ratios, put into drying drums, and
dry coated on the cereal product.
The following examples are of~ered to further illus-
l tr~te the improved process of this invention.
~
'''~"
ll .
1 32501 4
1 EXAMPLE 1
(Preparation of 1:1 Z~nc Meth~onine Complexes)
Thi3 proces~ prepares in batch form a 1,010 pound batch
_ of product. ~
Flve hundred pound~ of water are he~ted to ~ithin the
range of frsm 200F. to 205F. by ln~:ecting steam into a
batch holding stainle~s steel vessel. Three hundred pounds
of reagent grade zlnc sulfate are added to th- ve~ el, while
continually ~tirring the same. S~multan-ously lO~ounds of
ferric sulfate are added and st-am i9 continuously injected
in order to maintain the temperature withln the~range of
200F. to 205F. ~hereafter, 200 poundQ of methionine is ~ -
added, whils continuously stirri~g.
Immediately, the reaction product turn~ clear, all
1~ lumping i8 elminated, and the product appears to be a true
solution, redd~h brown in color. When lt is roadlly apparent
that everything i8 d1ssolved and nothing i~ in suspension,
the-product i~ then passed to a spray dryer and spray dried -~
to provide a 1:1 zinc methionine complex. ~
The formation of the 1:1 complex is confirmed by infra-
red ana1ysis, titration curve analysis, and quantitative -
l analysisO Such was found to be present ln excess of a 90%
i yield of the desired product.
25 ¦ EXAMPLE 2
(Formation of 1:1 Manganese Alpha Amino Acid
Complexes)
A substantially similar process as used in Example 1 is
done with the following changes. In this instance again the
¦1 am~unt of the batch was 1,010 pounds, 500 pounds of water,
_g_ ,
I
I ,
1 32501 4
1 and 500 pounds of ~olids. In the -olid~, the mangane~e ~alt
employed was man~ane~e sulfate, and the ferric catalyst
employed was again ferric ~ulfat~. ~he ount of mangane~e
sulfate employed wa~ 286 pounds, and the amount of methionine
employed was 214 pounds. The ratio of these *as 4:3. The
amount of catalyst employed wa~ 10 pounds.
Agaln, it wa~ evident that no lumping occurred, that
there was a true solution formed, and that the reaction was
nearly instantaneously complete upon stirring with the
reactants present. Again, the desired 1:1 manganèso methionine
complex was formed in a-yield in excess of 904.
It therefore can be ~een that the invention accomplishes
at least all of its ~tated objectives.
