Note: Descriptions are shown in the official language in which they were submitted.
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1 28505-1
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BACRGROUND OF THE INVENTION .
This invention relatec; to a method for making
an animal feed supplement and, in particular, a :~
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~` 1330272
molasses~based animal feed supplement in solid, block
form.
The value of molasses-containing supplements
as a palatable carbohydrate source and nutrient vehicle
in animal diets has been recognized for many years.
Phosphoric acid has often been added to the molasses
supplement to serve as a preservative and as a source
of dietary phosphorus. Urea has been added to animal
feed supplements to supply non-protein nitrogen, and
fats and vitamins have also been included as ingredi-
ents in animal feed supplements. Molasses-based feed
supplements are particularly valuable fed either
"free-choice'l to grazing cattle or to stock in confine-
ment where feed mixing facilities are lacking.
(Free-choice feeding allows the animal to consume from
a conveniently placed reservoir of liquid or solid
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;~supplement according to need.) Consumption during
free-choice feeding is controlled by use of a lick
~;20 wheel with liquids or by varying the hardness of a feed
block, both means limiting the animal's ease of
feeding. Controlling palatability of the feed block by
chemical means also limits consumption.
Solid animal feed supplements have been
prepared from molasses and other ingredients to augment
the dietary requirements of animals, especially cattle,
when forage is scarce or of low quality, for example,
during the summer months in California and summer
through winter in the Pacific Northwest. Solid feed
blocks offer the advantage of free choice feeding of
cattle, thereby reducing the labor and expense other-
wise incurred to mix the feed supplement with the
cattle's feed ration. Molasses blocks have been
manufactured by compressing ingredients into a molded
shape or by evaporative heating of the ingredients.
Both of these methods have certain disadvantages. For
example, energy-supplying ingredients, such as
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molasses, and heat-sensitive vitamins (if added) may
degrade during heating to the temperature necessary to
evaporate water.
Additional dietary requirements develop
during the seasonal periods when grasses are growing
rapidly, usually in the spring of the year. During
these periods, the magnesium content of grazing grasses
is so low that a condition of hypomagnesemia, commonly
known as grass tetany," often develops in grazing
herds. The condition manifests itself in the animal
; staggering or going into convulsions, and hypo-
magnesemia can even cause death in severe cases. The
situation is worsened if a high nitrogen or potassium-
content fertilizer is applied to the grassland to
encourage plant growth since uptake of magnesium from
~;~ the soil is thereby depressed.
To counteract the nutritional effects upon
~; grazing herds of grasses with low magnesium content,
animal feed supplements in the form of a liquid or a
solid block containing molasses and a concentration of
magnesium additive sufficient to overcome dietary
deficiencies of the nutrient have been provided.
Animal feed blocks containing molasses and magnesium as
a nutritional supplement have been disclosed by U.S.
Patent 4,234,608 to ~inehan wherein magnesium oxide and
dicalcium phosphate are reacted in molasses-containing
solution to form a solid feed block. U.S. Patents
4,171,385, 4,171,386 and 4,265,916 to Skoch, et al.
also incorporate magnesium oxide as a nutritional
source with or without the use of ferrous sulfate as an
additional blocking agent to form a moldable mixture.
However, magnesium oxide is highly alkaline and only
sparingly soluble in molasses so that mixing of so-
lutions containing magnesium oxide to maintain uniformdispersion requires great expenditures of energy.
Moreover, magnesium oxide, because of its sparing
1330272
-4-
solubility in molasses solutions, reacts slowly with
phosphate so that gelation requires at least one hour
and more commonly several hours.
As magnesium oxide is a highly basic sub-
stance, the animal feed supplements incorporating it as
a source of magnesium ions are usually highly basic,
having a pH in the range from about 9.5 to 11 pH units.
A particular disadvantage of alkaline animal feed
supplements containing nitrogen sources, such as urea,
is that grazing animals tend to produce free ammonia
from such feed during rumination. In a high pH en-
vironment, sufficient free ammonia can be produced from
the nitrogen source in the rumen of the animal to cause
ammonia poisoning leading to death.
In U.S. Patent 4,027,043, animal feed supple-
ments are disclosed which are prepared by mixing a
phosphate source and an aluminum or an alkaline earth
metal ingredient with molasses to solidify the resul-
tant mixture at an acidic pH. This patent disclosesthat the combination of a soluble phosphate or
phosphoric acid, at from 0.5 to 5 weight percent P2O5,
and an oxide or salt of aluminum, magnesium, calcium or
mixture thereof, at from 0.5 to about 5 weight percent
(expressed as the oxide) will solidify molasses.
The use of calcium chloride in liquid
molasses-based supplements for cattle and its effect
upon solidification has been investiqated by Grosso and
Nelson. (See "Calcium Chloride in Liquid Feed Supple-
ments" reported in complete texts of the speeches givenat the 1973 annual convention, NFIA-COUNTER '73,
October 14-16, 1973, Louisville, KY.) The object of
these investigators was to provide liquid supplements
with hign soluble calcium content and avoid solidifica-
tion; nevertheless, some of the formulations theyprepared did solidify. The formulations that did
solidify generally did not have a nutritionally
- 1330272
--5--
.:
appropriate amount of phosphorus, that is, they con-
tained either too much or too little phospharus and
they contained no magnesium additive. Certain of the
other formulations that had nutritionally appropriate
amounts of phosphorus did not harden since the phospho-
rus was supplied as a polyphosphate. (It has been
found in the present invention that polyphosphate does
not interact with calcium ions at acidic pH to provide
a solid product at nutritionally appropriate levels of
calcium and phosphorus concentrations or at convenient
temperature and mixing conditions. In addition, when
soluble salts of magnesium are introduced into molasses
feed supplements at nutritional levels, the mixture
will not gel at acidic pH to satisfactory hardness.)
One major problem in the making of animal
feed blocks results from the desire to transport and
store the feed supplement as a liquid, so that solid
blocks can be made from the liquid at remote locations
and/or in small lots as the need arises. Sometimes it
is more convenient to transport liquid solutions of
molasses-containing feed supplements to remote blocking
sites for storage than to transport and store molasses
blocks. But alkaline sugar solutions degrade rapidly
in storage. If the blocks can be rapidly and easily
solidified on demand from acidic liquid at remote
sites, blocks can be manufactured from the liquid
solution at will on site to meet the immediate nutri-
tional requirements of the herd by incorporating extra
vitamins, medicaments, and the like. However, to
accomplish this goal, the nutritional and blocking
agents added to molasses, especially the phosphorus,
magnesium and calcium, must be substantially soluble in
molasses or aqueous solutions. Molasses solutions
3~ prepared with less soluble ingredients, such as magne-
sium oxide, rapidly separate upon standing with the
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1330272
-6-
result that the solutions require constant stirring
with power mixers before molasses blocks can be made.
Therefore, when it is more convenient to manufacture
blocks from stored solutions as needed or to meet the
varying needs of the herd for vitamins, and the like,
it is desirable to have a method of rapidly and easily
preparing such solid feed blocks from substantially
homogeneous liquid solutions that gel rapidly.
10In addition, it is also desirable to have a
method for preparing acidic solid, molasses-based
animal feed supplements having nutritionally beneficial
contents of phosphorus, magnesium and nitrogen which
solidify rapidly when the ingredients are mixed at
convenient temperature and which do not subject grazing
herds to ammonia poisoning, but do counter the effects
;: of hypomagnesemia during seasons of rapidly growing
grasses.
. SUMMARY OF THE INVENTION
: 20An acidic feed supplement block is provided,
the block being formed from reaction of an acidic
liquid mixture comprising (a) a sugar-containing
source, such as molasses, (b) an orthophosphate source
or precursor, (c) magnesium, and (d) sufficient calcium
to provide a total calcium to magnesium weight ratio
between about 1.5 and 3.
The solid feed supplement is provided by a
method wherein (1) a liquid molasses mixture having an
acidic pH is formed by mixing two solutions, at least
one of which contains molasses or other sugar-
containing source, with the first solution containing
an orthophosphate compound, preferably orthophosphoric
acid, and the second solution containing a sufficient
amount of calcium to react with the phosphate compound
3~ in the presence of magnesium so as to form a solid
block, and (2) the liquid mixture is allowed to cure
and then recovèred as a solid-molasses-based feed
_7_ ~330272
supplement. To solidify the block, the weight ratio of
total calcium to magnesium in the liquid mixture is
usually standardized to between about 1.5 and 3 by
analytically determining the native content of magne-
sium and calcium in the mo:Lasses, which can differ
greatly depending upon the source of the molasses, and
adding sufficient additional calcium and magnesium to
achieve the desired weight rati~
BRIEF DESCRIPTION OF THE DRAWINC FIGURES
Figure 1 shows the variation in block hard~
ness with pH for cane molasses blocks containing
various amounts of added magnesium,
15Figure 2 shows the variation in block hard-
ness with pH for beet molasses formulations containing
various amounts of added magnesium,
Figure 3 shows the variation in block harden-
; ing with pH for molasses of low native magnesium
content at various total weight ratios of calcium to
magnesium,
Figure 4 shows the variation of block hard-
ness with pH at different total weight ratios of
calcium to magnesium.
: DETAILED DESCRIPTION OF THE INVENTION
Acidic feed supplement blocks are considered
advantageous for controlling the amount of the supple-
ment consumed by free-choice feeding grazing animals.
Overconsumption of blocks is both expensive and poten~
tially harmful to the animals, particularly in the case
of alkaline blocks. Acidic feed blocks minimize the
potential harm to the herd caused by overconsumption of
the feed supplement. Acidic feed supplement blocks
possess an additional advantage over alkaline blocks if
a non-protein nitrogen source, such as urea, is includ-
ed as a nutrient. In alkaline conditions, such
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- 1330272
-8-
nitrogen sources produce free ammonia in the rumen of
the grazing animal during rumination. Free ammonia is
readily ahsorbed into the animal's bloodstream and may
cause toxic symptoms or even death, if excessive.
Producing acidic feed supplement blocks has
proven surprisingly difficult, especially if concen-
trations of magnesium greater than about 1.0 weight
percent are present. Due to the chemical similarity
between magnesium and calcium, the latter of which is
routinely used to harden molasses blocks, it would seem
that magnesium could readily substitute for calcium as
a blocking agent. But it was discovered in this
invention that magnesium will not promote the proper
blocking (or curing) reactions under acidic pH con-
ditions, particularly of pH values below 4Ø However,
in acidic feed blocks containing the usual concen~
tration of calcium as a blocking agent, that is,
between about 1 and 2 weight percent of calcium, it was
surprisingly found that providing up to about O.S to
1.0 weight percent of magnesium produces a block having
superior hardness and water resistance.
It is yet another discovery in the invention
that, in a calcium-hardened block containing 1 to 2
weight percent of calcium, addition of sufficient
magnesium to meet the usual requirements for magnesium
as a nutritional supplement, that is, between about 1
and 2 weight percent of magnesium, destroys the hard-
ness of the bIock at acidic pH. However, it was most
surprisingly discovered that this problem could be
overcome by adjusting the calcium content so as to
provide a calcium to magnesium weight ratio between
about 1.5 and about 3Ø
Accordingly, the invention herein resides in
the discovery that acidic molasses feed supplement
blocks of superior hardness can be made by adjusting
the weight percent ratio of total calcium to magnesium
.
1330272
g
to fall within the range between about 1.5 and 3Ø
Within this ratio range, acidic blocks of superior
hardness and water resistance can be made that contain
magnesium in concentrations ranging from the small
amounts needed to impart heretofore unsuspected
synergistic blocking properties to a molasses mixture
to the greater amounts needed to meet nutritional
requirements for a magnesium feed supplement.
The present invention is most particularly
directed to magnesium-containing, acidic, molasses-
based animal feed supplement blocks having sufficient
water resistance and hardness to render handling
convenient, usually a hardness of less than 80
penetrometer units as measured by a standard grease
cone penetrometer (Precision Scientific Co.). The
penetrometer reading units are in 0.1 millimeter
increments of block penetration. The smaller the
readings, the harder the block. Preferably the feed
supplement block contains nutritionally beneficial
amounts of phosphorus and magnesium and, optionally,
non-protein nitrogen. Further, the invention resides
in a method for making the acidic molasses-based feed
supplement block by reacting two solutions under
conditions of agitation. At least one of the solutions
contains molasses, but the first solution contains the
phosphorus and the second solution contains the
calcium. The other ingredients, including magnesium,
are dissolved in either or both of the solutions but
preferably the magnesium is divided, although not
necessarily equally divided, between the two solutions
for improved solubility. In particular, care should be
taken to prevent super-saturation of either solution
with salts.
Differences in the gelling of molasses by
type and source of the molasses, such as cane molasses
from Hawaii and Central America or beet molasses from
1330272
--10--
California and Idaho, can be explained largely by
differences in the native content of magnesium and
calcium. A wide-ranging survey of sources of cane and
beet molasses indicates that native content of calcium
and magnesium may each vary between about 0 and 1
weight percent depending upon the location of the
source. Lot-to-lot uniformity within a single source
appears to be relatively stable. Generally speaking,
it has been discovered in the present invention that
the ultimate hardness depends upon the total weight
ratio of calcium to magnesium. Therefore, in accor-
dance with the invention, the gelling or blocking
responses at acidic pH among various strains of
molasses can be standardized (or controlled) by adding
sufficient calcium and/or magnesium to molasses to
bring the total weight ratio of calcium to magnesium in
the molasses into the range between about 1.5 to 3.0
which has been found to be critical for hardening at
low pH values.
One major problem is encountered in making a
feed supplement block containing enough magnesium to
counteract the effects of "grass tetany." In the
formation of the solid animal feed supplement, it has
been unexpectedly found that, while calcium ions
interact with phosphate ions to produce gelling of the
supplement sufficient to form a stable block, the
introduction of magnesium ions into the feed supplement
can interfere with the calcium-phosphate blocking
reaction sufficiently to make formation of solid feed
blocks containing this nutritional additive difficult.
It is believed that a competition between calcium and
magnesium ions for the available phosphate ions de-
stroys or weakens the blocking reaction. This diffi-
culty, whatever its cause, is overcome and a molassesfeed block of predictable hardness can be attained when
the total weight ratio of calcium to magnesium in the
1330272
liquid molasses mixture from which feed supplement
blocks are made is standardized to fall within the
range between about 1.5 and 3, preferably between about
1.75 and 2.25. By standardizing the weight ratio of
calcium to magnesium, a block having a hardness of less
than 80 in 0.1 millimeter penetrometer units, i.e. 0.1
mm = 1 unit, and containing any desired concentration
of magnesium or calcium within the limits of solubility
of the molasses used can be ohtained. ~As used herein
the total weight ratio includes both the native and the
added magnesium and calcium in the liquid reaction
mixture.)
In the present invention the ingredients of
the animal feed supplement are divided between two
liquid solutions such that, when mixed together, a
liquid mixture is provided containing all the desired
ingredients of the feed supplement block having a pH
below about 4.0 and a calcium to magnesium ratio
between about 1.5 and about 3Ø At acidic pH within
this range the resultant feed block has a hardness in
the desired range, i.e., below about 80 millimeters,
and preferably below about 50, and most preferably
below about 30 penetrometer units, and the thickening
liquid mixture has a viscosity similar to that of thick
cream so that it can be readily stirred. Moreover, the
gelation reaction proceeds rapidly in this acidic pH
range.
The desired ingredients for the animal feed
block are dissolved in either or both of the liquid
solutions, with one solution containing the phosphate
ion and with the other solution containing the calcium
in an amount sufficient to achieve the desired ratio of
calcium to magnesium in the final reaction mixture.
For convenience, it is usually preferred that the
molasses be divided equally between the two liquid
solutions to be mixed to form the reaction mixture.
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~12- 1 ~302 72
However, all the molasses can be introduced via the
phosphorus-containing solution with the other solution
being a brine containing the soluble calcium source.
Or the calcium source can be dissolved in the molasses
to comprise one solution while the phosphorus source is
dissolved in a second, aqueous solution. Othex ingre-
dients of the animal feed supplement as taught herein,
including magnesium, can be divided between the two
solutions or incorporated totally into either solution
as desired.
Because the ingredients of both the first and
second solutions are readily soluble in aqueous media,
including molasses, the solutions can be transported,
stored as separate solutions, and readily mixed
together at remote blocking locations as feed blocks
are needed. Stored separately, the solutions will
remain fresh for as long as about 7 to about 30 days,
or longer. When it is desired to convert the two
liquid solutions into a solid feed supplement, the two
solutions are introduced into a common mixing vessel,
such as a vat or even a mold of the shape desired for
the final solid block. After moderate to mildly severe
agitation for about 10 seconds to about 5 minutes, a
substantially homogeneous colloidal gel forms that
rapidly cures into a solid having the desired hardness
if the pH of the mixture of the two solutions is
maintained at a value below about 4.0 pH units. The
solution becomes viscous even during mixing and is firm
to the touch within a few hours. Within l to 5 days,
the solution solidifies to a hardness of 80 or less (as
determined by a standard grease cone penetrometer in
units of 0.1 millimeter) at which hardness it is easily
handled and transported. The solution may be allowed
to harden in the mixing container, for example, a
cardboard drum, or may be poured into another suitable
mold for hardenin~ or curing into a cube or cylinder.
1330272
-13-
Additional ingredients such as salt ~NaCl); protein
meals; non-protein nitrogen, such as, urea, biuret,
ammonium salts; fat; vitamins; trace minerals; and
medicaments and the like may be incorporated into the
resulting solid, molasses-based animal feed supplement
by adding such ingredients to the molasses solution
prior to hardening.
When introduced to fulfill nutritional
requirements, concentrations of ingredients in the
final ~eed supplement usually include between l and 2
percent by weight of phosphorus and between 1 and 2
percent by weight of magnesium. Concentrations of
calcium are usually determined by the requirements of
the calcium to magnesium ratio as taught herein, but
increasing the concentrations of both phosphorus and
calcium within the range of from l to 2 percent will
increase both the rate of hardening and the ultimate
hardness of the molasses blocks so long as the weight
ratio of the total calcium ion to the total magnesium
ion in the reaction ~mixture (including the native
calcium and magnesium in the molasses) remains within
the critical 1.5 to 3.0 range. Therefore, the pre~
ferred concentrations of both calcium and phosphorus
are within the range of 1.5 and 2.0 weight percent. At
acidic pH less than 4.0, a ratio of calcium to magne~
sium below about 1.5 or above 3.0 will result in
unsatisfactory gelation of the feed block. It is
especially important to utilize the above preferred
ranges of pH, ingredient concentrations, and calcium to
magnesium ratios when the total solids content of the
molasses-based animal feed supplement is low as when,
for example, a low BRIX molasses, for example below
about 75 BRIX, is utilized as the molasses source.
Molasses is commercially available as an
aqueous solution having a solids content rated at about
60 to 90 BRIX and a consistency varying from a thin
-14- 1330272
to a thick syrup. (Cane molasses is usually 80-90
BRIX. Beet molasses is usually 75-85 BRIX. Other
molasses, e.g. wood and citrus, may be lower, about
60-70 BRIX.) While molasses from different sources
may differ in both the identity and amount of non-sugar
and colloidal materials contained therein (such
non-sugar and colloidal materials may coprecipitate or
form solution aggregates with the calcium, magnesium,
and phosphate gel and thereby affect the rate of
hardening and the ultimate hardness), the molasses
utilized in the method of the instant invention may be
any sugar-containing molasses, such as cane or black-
strap molasses, beet molasses, corn molasses, wood
sugar molasses, citrus molasses, and the like.
Molasses having a solids concentration between about
;~ 60 and 90 BRIX can be used, but preferably, molasses
of higher solids concentration, for example, from 75
to about 90 BRIX, is utilized since a higher solids
content increases the ultimate hardness of the blocks
or requires less phosphorus, magnesium, and calcium to
; obtain equivalent hardness. The most preferred
molasses is cane or beet, since these are the most
abundant molasses available in commerce. The method of
this invention may also be used to solidify other
aqueous sugar solutions, such as refined sugar syrups,
although the lack of active non-sugar and colloidal
material in such aqueous sugar solutions may make
solidification less effective than with molasses.
The phosphate compound used to adjust the
phosphorus content of molasses to provide the
phosphorus-containing molasses solution may be any
suitable feed-grade, water-soluble phosphate or
phosphoric acid having a simple phosphate group, that
is, an orthophosphate. Polyphosphates, i.e., compounds
having more than one phosphate group condensed per
molecule, have been found to hinder the rate of
-15- 1330272
hardening and ultimate hardness of molasses solutions;
therefore, absence of polyphosphates is preferred.
While not wishing to be bound by theory, it is believed
that polyphosphate compounds sequester magnesium and
calcium ions and render them useless for hardening the
phosphorus-containing molasses solution. Similarly,
other calcium and magnesium sequestrants, such as
lactic and citric acid, should be avoided since they
either sequester ions or compete with the hardening
reaction of the calcium and magnesium ions and the
orthophosphate compound. Since sequestrants will
usually reduce the available calcium and magnesium in
proportion to their presence in solution, sequestrants
will usually have no effect upon the calcium to magne-
sium weight ratio of available ions. In addition
precipitants for calcium and magnesium should be
avoided, especially suIfate, which precipitates calcium
, .
ions. (Additional calcium and magnesium ions may be
provided to compensate for those sequestered or precip~
itated; however, this is economically inefficient.)
Useful phosphoric acids include electric
furnace (white) phosphoric acid, or defluorinated
wet-process (green) phosphoric acid, which can be of
any commercially available grade such as the commonly
available concentration range of from 50 to about 55
weight percent expressed as P2O5 corresponding to a
concentration of orthophosphoric acid of about 70 to 75
weight percent. Examples of water-soluble phosphates
which can be used are ammonium or alkali metal phos~
phates, such as mono- or diammonium orthophosphate,
monopotassium orthophosphate, etc. Polyphosphoric acid
can also be employed as a means to increase formula dry
matter since it easily dissolves in molasses or in
aqueous urea solutions or in any other aqueous solution
to be added to the molasses, provided sufficient time
is allowed at Iow pH for hydrolysis to orthophosphate.
-16- 1330272
The most preferred source of phosphate is orthophos-
phoric acid since it is an easily handled, high assay
liquid and is a readily available item of commerce.
When a phosphoric acid is used as the source of phos~
phate, typically 2 to 5% ammonium hydroxide (29~ NH3)
is needed to provide the opti~num pH. Finally, ortho-
phosphoric acid functions as a preservative, fly~
repellant, intake control agent and is a pH modifying
agent for ammonia produced during urea digestion by
ruminant animals. In addition, certain other sources
of orthophosphate are suitable, such as mono- and
disodium phosphate and calcium dihydrogen phosphate.
As discussed above, the orthophosphate
compound is added to the molasses in an amount suffi-
cient to provide from l to 2 weight percent, preferably
1.5 to 2 weight percent of phosphorus (calculated as P)
in the final solid product. Less than about 1 weight
percent of phosphorus in the solid, molasses-based
animal feed supplement is inadequate for a solid block
formation and is marginal from a nutritional
standpoint. Although phosphorus contents greater than
about 2 weight percent may be used, such high concen-
trations may exceed nutritional requirements for
cattle, at typical block consumption rates. Therefore
it is not appropriate from an economic standpoint to
exceed 2 weight percent of phosphorus. Also, the
hardness of the solid molasses blocks produced by the
method of this invention is not increased appreciably
by the excessive phosphorus.
For best results the magnesium source is
water soluble so that reaction with phosphate and
soluble calcium during gelation proceeds
simultaneously. Therefore, magnesium compounds, such
as magnesium oxide, insoluble in virtually all aqueous
media are unsuitable for use in the composition and
method of this lnvention. Typically, magnesium
-17- 1 330272 :
:,...
chloride, as well as the magnesium salts of the lower
molecular weight organic acids, for example, magnesium
acetate and magnesium propionate, may be used, as well
as other magnesium-enriched pxoducts, such as magnesium
lignosulfonate and magnesium sulfate. Of the above
magnesium compounds, magnesium chloride is the most
preferred since this source of magnesium ion is inex-
pensive and very soluble in water, aqueous urea so-
lutions, and sugar syrups such as molasses. Mixtures
of the above magnesium salts are also conveniently
used. The amount of magnesium employed, including the
native magnesium, is usually from about 0.5 to about
2.0 weight percent of the solid molasses block of this
invention, expressed as magnesium, and preferably is
from about 1.0 to 2.0 weight percent for nutritional
purposes.
The calcium source is usually water soluble
although compounds such as calcium oxide, which is
soluble in molasses but not in typical aqueous media
may be used in the invention. Preferably, calcium
chloride, as well as the calcium salts of the lower
molecular weight organic acids, for example, calcium
acetate and calcium propionate, are used, as well as
other calcium-enriched products, such as calcium
lignosulfonate. Of the above calcium compounds,
calcium chloride is the most preferred since this
source of calcium ion is inexpensive and very soluble
in water, aqueous urea solutions, and sugar syrups such
as molasses. Mixtures of the above calcium salts are
also conveniently used. The amount of calcium employed
depends upon the total amount of magnesium in the
reaction mixture. Sufficient calcium is added so that
the weight percent ratio of calcium to magnesium falls
within the range between about 1.5 and about 3, pref~
erably between about 1.75 and 2.25. Like the phospho-
rus content, the preferred calcium ion concentration,
-18- 1330272 -:
for rate of hardening and ultimate hardness, also
depends on the total solids of the molasses-containing
animal feed supplement.
It has been found that in the pH range below
about 4.0 pH units maximum hardness for the solid
molasses feed supplements of this invention is attained
when the total ratio of calcium ion to magnesium ion
per weight basis in the product feed block is between
about 1.5 and 3, and preferably between about 1.75 and
2.25. Therefore, after determining by conventional
analytical methods the native concentrations of magne-
sium and calcium in the molasses to be used, sufficient
amounts of each are added so that the calcium and
magnesium concentrations in the final reaction mixture
(and resultant feed block composition) fall within the
critical range of calcium to magnesium ratios necessary
to promote rapid gelation and desirable hardness.
The calcium solution may be added to the
phosphorus-containing molasses as an aqueous solution
or brine. Or calcium and magnesium may be added as
; components of any other aqueous liquor to be added to
the phosphorus-containing molasses solution, for
~;~; example, with the aqueous urea solution. With high
shear input, calcium chloride and/or magnesium chloride
might be incorporated in dry form, such as flakes
High shear is required to disintegrate and disperse the
solid flakes. Preferably, for ease of mixing, the
calcium and magnesium are predissolved in molasses.
Most preferably a molasses solution containing from
about 2 to about 4 percent calcium is prepared to be
-~ combined with an equal volume of a phosphorus-
containing molasses solution.
The pH of the reactant solution, that is, the
solution resulting from combining the phosphorus~
containing solution with the solution containing the
calcium source, is adjùsted to a value preferably less
~` '
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1 33 0272 ~ ~
--1 9-- ,, ~
than about 4.0~ more preferably less than 3.75, and
most preferably between 1.5 and 3.75 pH units using a
pH-modifying agent. The pH- modifying agent can be
either acidic or basic as needed to adjust the pH
within the desired range, depending upon the initial pH
of the solution. For example, if orthophosphoric acid
iS used as the phosphorus source, as in the preferred
embodiment, a basic pH-modifying agent, either as an
aqueous solution or anhydrous, preferably ammonia, can
be used to adjust the pH. Other water-soluble bases
may be used, such as the alkali metal hydroxides, for
~-~ example, sodium and potassium hydroxides. Ammonia is
preferred for its low cost and because it contributes
to the protein equivalent of the resulting solid animal
feed supplement by providing nitrogen that can be
converted to amino acids by ruminant feeders. If an
~; acidic pH modifying agent is required, hydrochloric and
acetic acids are inexpensive to use and are, therefore,
preferred, but any water-soluble hydrogen ion source
can be used. However sulfuric acid is usually used
~` sparingly to minimize the presence of sulfate in the
reaction mixture.
The pH is measured after homogeneously
combining all of the ingredients utilized in the solid
molasses blocks of this invention. However, if the pH
is to be adjusted with ammonia, such adjustment is
usually made prior to addition of the calcium source.
Adding ammonia to a solution containing added calcium
ions produces an inferior solid, molasses-based animal
feed supplement due to formation of precipitates at
localized areas of high alkalinity prior to uniform
dispersion of the alkaline ingredient. Therefore, if
calcium chloride, either as a solid or as an aqueous
solution is the source of calcium, the pH of the
phosphorus-containing solution i~ preferably adjusted
to somewhat greater than the pH of the resulting
-20- 1 3 3 02 72
reactant solution with ammonia so that, when ultimately
combined with the phosphorus-containing solution, the
desired pH is attained in the reaction mixture.
In the preferred embodiment described below,
a calcium-containing molasses solution i5 combined with
a separate phosphorus-containing molasses solution.
Therefore, in this embodiment the orthophosphate is
dissolved in a first molasses solution at a concen-
tration higher than 2 percent by weight, and the excess
phosphorus content is diluted to the correct concen~
tration by the calcium-containing molasses solution.
For example, if equal volumes of the orthophosphate-
containing molasses solution and the calcium-containing
molasses solution are to be combined to provide a solid
product, then from 2 to 4 percent, by weight, phospho-
rus is dissolved in the first molasses solution to
yield a product containing 1 to 2 weight percent
phosphorus.
In the preferred me~hod, phosphorus is
pre-dissolved in a first molasses solution, mixed with
~; a second, calcium-containing molasses solution, and the
pH of the phosphorus-containing molasses solution is
adjusted to provide a reactant solution having a pH
upon combination of the two molasses solutions as
specified above. The magnesium source may be dissolved
in either or both molasses solutions.
The optimum pH for any given molasses is the
acidic pH at which the molasses feed supplement block
achieves greatest hardness and varies somewhat from one
molasses to another. Although molasses feed supple~
ments containing the desired nutritional amounts of
nitrogen, phosphorus and magnesium can be gelled at
higher pH values, for example at around 4.5 pH units,
and above, the supplement mixture becomes so viscous
~the consistency of paste) at such elevated pH values
that mixing requires factory scale equipment. In
-21- 133~272 :: :
addition, the expense of energy and equipment required
to stir a highly viscous liquid is uneconomical. In
any event, where small scale mixing operations are
contemplated, for example at remote blocking locations,
operation in the pH range below 4.0 using the calcium
to magnesium ratios required in this invention enables
the use of small scale mixers capable of providing no
more than moderate to mildly severe agitation to
solutions of moderate non-Newtonian viscosity (the
consistency of thick cream).
The result of nonuniform dispersion is a
nonhomogeneous product which may have localized fluid
and solid regions. But shearing agitation, as obtained
with a ~ightnin Mixer, is adequate to prepare small
laboratory batches of the mixture of the two solutions;
however, prolonged shearing or remixing after 15 to 30
minutes standing should be avoided sinc~ the gel formed
by the interacting orthophosphate, magnesium, and
calcium ions may be disrupted prior to setting into a
hard product. Hand-mixing of small batches has even
been found to be adequate if the calcium and magnesium
are predissolved in a molasses solution. In general,
mixing for 10 seconds to 5 minutes with a Lightnin
Mixer or 1 minute to 5 minutes by hand is adequate to
combine the phosphorus-magnesium molasses solution with
~` a calcium-magnesium molasses solution, as in the
i ~ preferred embodiment, so as to render a uniform gel
that will cure into a solid product.
However, if the calcium is added as a brine,
for example an aqueous solution containing 50 percent
by weight of calcium chloride, more intense mixing may
be required. It may be desirable to avoid the addition
of water, particularly when using a high water content
molasses to achieve increased hardness in the resulting
solid molasses blocks. Thus, calcium chloride (or
other source of calcium ion) might be added as a solid
. ., ::: :, .
~, :.: . ,:,
.:, -.. .:.~:
-22- 1330272
or a very concentrated solution. But in this embodi-
ment, high shear mixing, as from a turbine or centrifu-
gal pump or an in-line mixer, may be required. In a
continuous operation an in-line mixer, for example, a
high speed rotor, inside a flow-through tube is
suitable.
The phosphorus and calcium-containing so-
lutions described above may be mixed in the mold used
to form the solid product of this invention or the
resulting mixture may be mixed and then poured or
otherwise introduced into molds. The mixt~re will
thicken rapidly upon combining the two solutions so
that at most within 30 minutes after the ingredients
have been combined the mixture should be poured into
forms selected to impart the desired solid block form.
Any size molds can be used, but for ease of handling,
molds providing solid blocks of from 30 to about lO0
pounds, preferably from about 50 to about 55 pounds,
can be used. But blocks as large as 500 pounds or
greater can also be manufactured using this method.
These blocks can be cylindrical, cubic, or any other
suitable shape. In one embodiment, the thickening
mixture is introduced into corrugated cardboard boxes
~;~ 25 which are closed, sealed, and stored for a sufficient
time to permit the liquid to solidify or cure, typical~
ly for a period of 1 to about 5 day~. After the blocks
have cured, the resultant packages can be palletized,
and the like, for shipment and storage.
The temperature at which the above solutions
are combined, as well as the temperature at which the
resultant solution is cured, affects the hardening
rate. In general, increasing temperature facilitates
mixing and increases the curing rate. For example, it
has been found that if the molasses blocks are cured at
4 C., maximum hardness is attained after 3 to 4 weeks
of curing, but when cured at 21 to 27 C., maximum
, . .,;
133~272 i
-23-
. .
hardness occurs after 5 to 7 days, and at 41 C. only 1
to 2 days are required to attain maximum hardness.
Preferably, the resulting mixture is agitated and
subsequently cured at a temperature of from 16 to
43 C., more preferably at from about 24 to about
43 C. A higher temperature, within the above range,
will provide benefits for the mixing step of this
invention in two ways. First, the resulting decrease
in the fluid viscosity of the mixture makes for better
mixing. Second, the rate of hardening of the mixture
is increased by increasing temperature. ParticuIar
advantage of the temperature effect in the mixing step
can be taken by using solid calcium chloride and/or
other additives that provide a significant heat of
solution, such as anhydrous additives, to raise the
temperature of the reaction mixture. To take advantage
j~ of these temperature effects in colder climates, one or
both of the aqueous solutions can be preheated, and the
liquid-containing molds can be stored in a heated area
during the curing period. However, care should be
taken to avoid temperatures in excess of about 43 C.
since molasses decomposition may ensue at temperatures
above that point.
The solid, molasses-based animal feed supple-
ments prepared by the method of this invention desir~
ably include other nutritionally suitable ingredients.
For example, fats and oils may be employed in the
invention as a source of animal edible fat. Option-
ally, edible fats and oils from animal and vegetable
sources ~which can be liquids or solids at room temper-
ature) can be included in the solid, molasses-based
animal feed supplements of this invention. The solid
` compositions can contain from 2 to about 30, preferably
from 5 to about 20, weight percent of edible fat.
These fats include various fatty acids, such as
stearic, palmitic, oleic, linoleic, and lauric, and the
' ':
~`~' ~: '. ',
~ 1330272
-24-
mono-, di-, or triglycerides of these fatty acids.
Useful fats and oils can also include complex lipids,
such as the phospholipids, for example, fatty acid
esters of glycerol, phosphate or lecithins, which also
contain nitrogen bases, such as choline. The fats are
commonly identified by source and suitable fats which
can be employed include the oils, tailings, or refining
residues from the following sources: soybean oil,
cottonseed oil, sesame oil, rapeseed oil, olive oil,
corn oil, tallow, fish oil, coconut oil, and palm oil,
and the like. Preferably, relatively inexpensive
sources of fats are employed, such as yellow grease
compositions, restaurant fats and greases, acidulated
soap stocks or acidulated fats and oils. Such fats may
also contain an antioxidant in an effective amount to
inhibit oxidative degradation of the fat, for example,
from 0.01 to about l weight percent of butylated
hydroxyanisole, butylated hydroxytoluene, 4-hydroxy-
methyl-2, or 6-di-tert butylphenol, among others.
An emulsifying agent can be included to
stabilize the composition and prevent separation of the
fat ingredient during storage of liquid solutions and
manufacture of the product. Weeping of the fat ingre-
; 25 dient from the solid ~lock after its formation can also
be prevented by employing an emulsifying agent at a
concentration of from about 0 to about 2 weight
percent. Preferred emulsifying agents are the
colloidal clay gellants, for example, attapulgite,
bentonite, and sepiolite, which also function toincrease the hardness of the solid product of this
invention.
The solid, molasses-based feed supplement of
this invention also may contain a nonprotein nitrogen
source, such as ammonia, urea, biuret or mono- or
diammonium phosphate to supply a part of the nitrogen
dietary requirements for ruminants. (Note that ammonia
1330272
-25-
may also be used for pH adjustment and ammonium phos-
phate may provide orthophosphate. Thus, these sources
of nonprotein nitrogen are dual functional.) The
preferred nonprotein nitrogen isource is urea, which can
be added to provide a concentration from about 1 to
about 15 weight percent, and preferably from about 5 to
about 10 weight percent based on the solid, molasses-
based feed supplement of this invention. Generally,
10 the feed supplement will contain no more than about 40 ~
weight percent equivalent protein content from a ~ -
nonprotein nitrogen source. Since the molasses also
contributes from 1 to about 3 weight percent of
utilizable nitrogen, the maximum amount of urea or
other nonprotein nitrogen source may be reduced by the
amount of nitrogen contributed by the molasses.
Various trace nutrients, drugs, and vitamins ~ .
~;can also be incorporated in the solid, molasses-based
animal feed supplements of this invention, including
vitamins A, D, and E, tocopherols, as well as
antioxidants for these materials, such as ethoxyquin
(1, 2-dihydro-6-ethoxy-2, 2,4-trimethyl quinoline).
Appropriate medicaments may be incorporated on an
"as-needed" basis. The quantity and concentration of ~`
25 these medicaments must, of course, be in accord with ~ 5
established FDA regulations governing their use.
The following table sets forth the typical ~-
concentrations of ingredients for the compositions of
the invention~
-~
: ' ''
~' '
~
':
~ ~ .
'~
-26-1~3027~
..
TABLE I
COMPONENT (Wt.
1. Molasses 60-87
2. Fat 0-30
3. Orthophosphate 1 2 ~ .:
(as P) ~ ~:
4. Calcium 1-4
(as Ca) (as required for Ca:Mg
from 1.5 - 3.0)
5. Magnesium 0.5-2
.. :
15 . 6. Emulsifier 0-1 ~ :
7. Starch, clay or other 0-2
thickeners or gellants
8. Equivalent Protein derived 0-40 :~
; from non-protein nitrogen
sources ~ ~
9. Trace Minerals, vitamins 0-1 ~ ;
10. Salt (NaCl or KCl) 0-10
11. Medicaments (as approved)
~ ~ 12. Basic or Acidic Materials (as required)
; 25 for pH adjustment
.:::: .; . -
The above ingredients are preferably combined
with molasses or with either of the aqueous solutions
prior to pH adjustment since certain of these ingredi-
ents will have pH effects of their own.
The invention is further illustrated by the :
following exampIes which illustrate specific modes of
practicing the invention and are not intended as
limiting the scope of the appended claims. Unless
stated otherwise, the ingredients are in gram units and
th- percents are welght percents. Where a solution is
`~ '
.~:
-27- 13302~12
referred to, it is understood that the solution is
aqueous.
EXAMPLES 1 AND 2
__
To compare the hardness characteristics of
typical molasses block compositions containing varying
amounts of magnesium, two molasses block systems were
studied, one using cane molasses and one using beet
molasses. In each molasses block system, the formu-
lation contained about 70 weight percent molasses, 1.5
weight percent of phosphorus from orthophosphoric acid,
1.5 weight percent of calcium from calcium chloride, 20
weight percent of protein equivalent from urea (and
- ammonia used to adjust pH), and 0 to 5 weight percent
of sodium chloride along with sufficient magnesium
chloride to provide magnesium in zero, 0.5, 1.0 and 1.5
weight percent concentrations in the cane molasses
system and zero, 0.5 and 1.5 in the beet molasses
system.
Equal weight portions of the calcium-molasses
and phosphorus-molasses stock solutions (shown in Table
2) were blended using a Lightnin mixer to maximize
colloidal dispersion of the reacted ingredients. The
mixture was poured into 200 gram molds and cured for
two days at 41~ C. followed by one day at room temper-
ature. Hardness values were measured using a Precision
standard grease cone penetrometer having a cone weight
of 102.5 grams. The units of the penetrometer readings
are in 0.1 millimeter~increments of penetration into
the molasses block by the tip of the penetrometer's
cone. The same method of mixing, curing, and measuring
hardness is used throughout the Examples herein.
Formulations used in Example l, the cane
molasses system, are summarized in Table 2 for the 0.5
weight percent added magnesium level. As shown in
Figure l for this cane molasses system containing 1.5
weight percent of calcium, the optimum hardness of less
-2~- ~330272 ;:
than 30 units occurs at a pH of about 3.5 when the
total calcium to magnesium ratio is 2.4. Hardness of
about 40 units i5 also achieved at a pH slightly less
than 3.5 with a calcium to magnesium weight ratio of
about 1.5. Hardness falls off sharply when the calcium
to magnesium weight ratio is 1.1, which lies outside
the required range of 1.5 to 3
By contrast, the formulation containing no
added magnesium achieves maximum hardness at a pH
between 4.0 and 4.5. In this pH range the reaction
; mixture has the consistency of paste and requires
expensive mixing equipment to prepare so that prepara~
tion of feed supplement blocks at remote sites is
thereby rendered impracticable. In addition, it should
be noted that, although this formulation achieves the
requisite hardness, it contains no added magnesium.
The native calcium and magnesium contents of the cane
molasses used here are 0.63~ Ca and 0.44% Mg.
TABLE 2
FORMULATION FOR EXAMPLE 1
.
P StockCa Stock
Wt. % Wt. %
50~ Urea Solution 11.0 11 0
Phosphoric Acid ~23.8% P) 12.6
Cane Molasses ~84 BRIX) 70.6 70 9
Calcium Chloride (29.2% Ca) ---- 10 3
Magnesium Chloride Brine 5.8 5.8
(8.6% Mg.) -;~
Water ---- 2.0
29% ammonia added for pH adjustment.
Example 2 uses a beet molasses block formula
substantially identical in formulation to the cane
molasses system of Example 1, as is shown in Table 3.
The native contents of calcium and magnesium are 0.3
weight percent of calcium and 0.19 weight percent of
-29~ 1330272 ~
magnesium. The reaction liquid was prepared by mixing
in equal weight proportions a first solution containing
the ph~sphorus and one-half of the magnesium and a
second solution containing the calcium and the other
one-half of the magnesium. Formulations for these
solutions are summarized in Table 3 for 0.75 weight
percent of added magnesium.
In the absence of magnesium, optimum hardness
occurs over a very narrow pH range (about 2.9 to 3.0,
pH units). However, with addition of magnesium and
adjustment of the calcium to magnesium ratio to fall
within the required range, hardness increases and the
effective pH range broadens, ranging from about 3.0 to
4 0 pH units. In this system, maximum hardness occurs
when 0.75 percent magnesium is used and the pH is about
3.5.
TABLE 3
FORMULATION FOR EXAMPLE 2
P Stock Ca Stock
Wt. % Wt. %
50% Urea Solution 10.0 10.0
Phosphoric Acid (23.8% P) 12.6
Beet Molasses (81 BRIX)68.7 69.0
Calcium Chloride (29.2% Ca) ---- 10.3
25 Magnesium Chloride Brine 8.7 8.7
(8.6~ Mg.)
Water ---- 2.0
29~ ammonia added for pH adjustment.
EXAMPLE 3
To determine the blocking effects of added
magnesium without contribution from native magnesium in
the molasses, a molasses system was formulated using
beet molasses containing very low calcium and magnesium
35 (less than 0.01 weight percent magnesium and 0.04
weight percent calcium). The formulation for this
system is shown in Table 4. The calcium to magnesium
., :: '
1330272
-30-
ratio of this beet molasses formulation containing no
added magnesium is very high, greater than 123.
! -
TABLE 4
FORMULATION FOR EXAMPLE 3 (NO ADDED MAGNESIUM)
P Stock Ca Stock -~-
Wt. % Wt %
_
50% Urea Solution 10.0 10 0 ~ -
10 Phosphoric Acid (25.4% P) 11.3
Salt 10 0 ----
Beet Molasses (87 BRIX)61 4 68.3
Calcium Chloride (29.2% Ca) ---- 8 4
Water 6.8 13 3
29% ammonia added for pH adjustment.
A second formulation was prepared from the
same beet molasses to contain 1.5 weight percent
phosphorus, 1.2 weight percent calcium, and 0.6 weight
percent of added magnesium, giving a weight ratio of
calcium to magnesium of about 1.9. The formulation for
; 20 the beet molasses system containing added magnesium is
shown in Table 5.
~ . :
TABLE 5
FORMULATION FOR EXAMPLE 3 (ADDED MAGNESIUM) ~ ;
P Stock Ca Stock
Wt. % Wt. %
50% Urea Solution 10.0 10.0
Phosphoric Acid (23.8% P) 12.6
Salt 10 0 ---- --
30 Beet Molasses (87 BRIX)58 2 65.6 : ~-
Calcium Chloride (29.2~ Ca) ---- 8.4
Magnesium Chloride Brine7.1 8.0 :~ -
(8.6% Mg.)
Water 2.1 8.0 .-
- . ,-
29% ammonia added for pH adjustment.
As illustrated in Figure 3, the formulation
containing no added magnesium (Table 4) yields a block
. ~.. ,~,
': ' '' ''' ~ '
~, .....
` 1330272
-31
having increasing hardness with decreasing pH, but the
hardness for those pH values tested was consistently
less than the comparable magnesium-containing formu~
lation. By contrast, the formulation containing 0.6
weight percent of added magnesium (Table 5) yields a
block having a hardness of about 30 units when the pH
is about 3.5. At lower pH, the hardness of the block
falls off. This example shows that by adjusting the
calcium to magnesium weight ratio to 1.9, an acid
magnesium-containing molasses block can be obtained
having a hardness of about 30 units, which is much
harder than the block containing no magnesium.
-': ~ '..'
EXAMPLE 4
To demonstrate that within the critical pH
range gelation depends upon maintaining a favorable
ratio of calcium to magnesium rather than upon the
content of calcium or magnesium alone, the inferior
formulation from Example l containing 1.5 weight
percent of magnesium was improved by adding sufficient
calcium to bring the calcium to magnesium weight ratio
to 2, the preferred value within the critical range
between 1.5 and 3. As can be seen in Figure 4, hard-
ness of the block formed from the most unsatisfactory
formulation illustrated in Example l was restored, with
the hardest block ~having hardness of about 31 units)
being formed from an improved liquid solution having a
pH of about 2.7. Formulations used in Example 4 are
summarized in Table 6.
This example illustrates that levels of
magnesium high enough to meet nutritional requirements
(i.e., above 1.0 weight percent) can be incorporated
into a molasses block formulation without causing
undesirable softening of the block if the weight ratio
of calcium to magnesium (including native calcium and
1330272
-32-
magnesium in the molasses) is adjusted to maintain a
value within the critical range. ~-
5TABLE 6
FORMULATION FOR EXAMPLE 4 ~:
UNIMPROVED BLOCK ~ .
(Ca/Mg Wt Ratio~
P Stock Ca Stock
Wt. % Wt. ~ ~, r~,~
50% Urea Solution 11.0 11 0
Phosphoric Acid (23.8% P)12.6 -- -
Cane Molasses (84 BRIX) 59.0 59.3
Calcium Chloride (29.2% Ca.) ---- 10.3
Magnesium Chloride Brine 17.4 17.4
- (8.6~ Mg.)
15 Water _ _ 2.0
.
29% ammonia added for pH adjustment.
IMPROVED BI.OCR
(Ca/Mg Wt. Ratio 2.0) ~ -~
P Stock Ca Stock B
Wt. % Wt. %
50% Urea Solution 11.0 11 0
Phosphoric Acid (23.8% P)12.6 -- -
Cane Molasses (84 BRIX) 59 7 46.2
CaIcium Chloride (29.2% Ca.)-- - 21. 5
Magnesium Chloride Brine 16.7 16 7 -~
(9.0% Mg.)
Water ---- 4.6 ~ -
29~ ammonia added for pH adjustment. .-
EXAMPLES 5--12
To determine the best method for measuring ! -
the pH of hàrdened molasses blocks, pH results from two```
~methods of measuxement were compared with the~pH values -
~- ` of the fresh liquid mixture from which each bIock
tested had been solidified. By the first method, the
pH of a 50 weight percent water slurry of the hardened
block was measured. By the second method, a surface of ~;
the hardened bloak was dampened just enough to get a pH
~, . .
\ : :
-~`` 1330272 ~ ~;
28505-1
reading ~nd the reading was recorded. Measurements
were made using Corning Model 145 digital pH meter
a~fixed to an Orion Combination Electrode No. 91-36
5 having a flat battom. ;~
Readings were made for two sets of molasses ~;
block~, the first set containing no added magnesium but
containing 2.6 weight percent of added calcium and 1.6 -~
weight percent of added phosphorus. The second set of
blocks has the relatively high content of added magne~
sium of 1.5 weight percent and also contains 3.1 weight
percent of added calcium and 1.5 weight percent of
added phosphorus. Results o~ the pH tests are sum-
marizsd in~Ta~le 7.
TABLE 7
COMPARISON OF pH DETE~MINATION MET ODS
GROUP A - NO ADDED M~G~ESIUM
20 Example pH of Fresh pH of 50 Wt.% pH of Dam~
No.Liauid Mixturewater Slur~v Bloc.
2.7 3.4 2.8
6 3.8 4.0 3.6
7 4.5 4.7 4.6
8 5.2 5.6 5.4
25-
G~OUP B - 1.5 WT. PERCENT ADDED MAG~ESIU~
Example pH of Fresh pH of 50 Wt.~ p~ of Dam~
No.Li~uid MixtureWater Slurrv Bloc.~
9 1.9 3.0 2.3
; 30 10 2.5 3.6 2.g ~- ;
11 3.1 4.4 3.9 .
12 4.1 5.4 4.~ -
As can be seen from ~he data in Table 7, ~or
all molasses containing blocks, when ?H of the block is -
determined by making a 50 weight percent water slurry
from the solid block, p~ readings are substantially
higher than when p~ of the block is determined directly
*Trade-mark
. .
/ ` : -34_ 133~272
by dampening its surface sufficiently to get a pH
reading with a flat-bottomed electrode. This is as
would be expected considering dilution of the salts
present. The differences are most pronounced in the
high magnesium, high calcium salt series. Thus, it has
been determined that dampened surface pH measurements
of hardened blocks are in close agreement with the
fresh product liquid and should provide a reliable
quality checkpoint. Also, in this invention the pH of
the hardened block is determined by dampening the
surface of the block to measure the pH.
It will also be noted from the data that the
liquid-block pH differential is greater when the block
has a large magnesium content than when no magnesium
has been added to the block. For this reason the pH of
the liquid mixture should usually be adjusted from 0.4
to 0.8 pH units lower than the desired pH of the
product high magnesium block.
" '`
While particular embodiments of the invention
have been described, it will be understood that the
invention is not limited thereto since many obvious ;;
modifications can be made. It is intended to include
within this invention any such modification as will
fall within the scope of the appended claims.
"~"~;';"'''"
30 ~ ~ -
.. . .
35 ~ ~;
` ."~ .:
