Note: Descriptions are shown in the official language in which they were submitted.
107507S
The present invention relates to a stabilized fodder
preserving solution containing formaldehyde.
It is well known that formalin combined with other sub-
stances can be used as a fodder preserving agent. The diminish-
ing effect of formalin on the conservation losses and the improv-
ing effect on the nutrient utilization are also well-known. The
problems have been the polymerization of formaldehyde in solutions,
although formalin often contains for instance methanol as a poly-
merization inhibitor, and also the low flash point, particularly
in solutions where inorganic acids have been used, such as sul-
phuric acid, hydrochloric acid,-phosphoric acid.
A known and also experimentally tested method is to mix
formalin and acid each from separate vessels at an individually
adjusted ratio only at the preparation stage of the preserved
fodder directly into the fodder by means of a separate mixing
device.
However, this has not proved to be a usable method in
practice primarily because of the polymerization of the formalin
and the difficult handling of the strong acids. Furthermore,
formalin and acid used together in the same solution give a better
result than each substance used separately.
The amounts of acid in the present preserving solutions
containing formalin have gener~lly been rather small, only about
:
~k
,
. . .
. ~ ~
1~75075
3 to 5 acid equivalents per liter.
In order to ensure a better conserving effect it would be
appropriate if the amount of acid could be increased, in which
case the pH of the fodder would be more certain to decrease.
According to recent investigations a comparatively strong pH
decrease together with the conserving effect of formalin gives,
so far as a fodder preserving solution is concerned, the best possible
result. If the acid used is for instance hydrochloric or sulphuric
acid, an increase in the amount of the acid has further the advan-
tage that the cost of the product will decrease correspondingly.
Furthermore, the present fodder preserving formalin containing
solutions contain predominantly formalin, e.g. in the ratio of 1
part of acid to 2 parts of formalin (so called Viher-solution
(Farmos Oy)), which is described in the Finnish patent no. 43941,
and Sylade (Imperial Chemical Industries), which is described in
the Finnish patent application no. 3276/72, according to which
even 9 parts of volume of formalin to one part of volume of acid
may be used.
Unexpectedly it has now been found that the proportion of
formalin in the preserving solution may be substantially decreased
without the advantageous conserving effect of formaldehyde diminish-
ing~ as far as the fodder quality and the conserving of nutrients
are concerned.
At the same time laboratory experiments have surprisingly shown
that the preserving solutions containing formalin can be made to
stay clear if the ratio of formalin and acid is kept within compa-
ratively narrow limits which limits also in preservation experiments
have proved considerably more advantageous than those prior used.
The invention concerns stabilized fodder preserving solutions
containing formaldehyde, the characteristics of which appear from
the appended claims. The stabilized solutions comprise formalin ~-
and inorganic or organic acid~ whereby as inorganic acids pre-
ferably hydrochloric, sulphuric and/or phosphoric acid and as or-
ganic acid preferably formic acid, or their mixtures, come into
question. The limits within which the preserving solution has both
a good conserving and stabilizing effect is formalin : acid =
1 : 1.2 to 1 : 2.5 by volume whereby the solution contains 8.5
to 13.5 equivalents of acid per liter solution.
- 2 -
1075075
By formalin is meant a 35 to 40 % aqueous formaldehyde solu-
tion containing methanol and to which is further added e.g. carboxy
methyl cellulose~ hydroxy ethyl cellulose, vinyl acetate telomer,
or some other known formaldehyde stabilizer.
Irrespective of the stabilizing agent initially added to the
formalin~ about 1 to 2 per cent by weight of urea is added to the
preserving solution according to the invention, preferably dissolved
in water before mixing.
By stabilization is meant that the solution stays clear within
a wide temperature range (from room temperature to -20C~ the flash
point at the same time staying sufficiently high.
According to the statute no. 335/54 concerning flam~able liquids,
a liquid the flash point of which is below 55C is considered to
belong to the group of flammable liquids. By means of the stabilized
composition according to the invention not only is the polymerization
prevented but also a sufficiently high flash point is ensured.
To the above mentioned stabilization problem chemists have for
years tried to find a simple, economical, and practical solution,
however, without any success. With the preserving solution according
to the present application it has been possible to solve these prob- -
le~s in a way that is rather surprising even to those highly
skilled in the art.
The following examples and tables illustrate the invention as
to the stabilization of the solutions. The percentages imply per
cent by weight if not otherwise indicated.
Example 1
- 27.9 parts by vol. of formalin, which contains 37% formaldehyde
and 4.8 % methanol,
- lO - " - stabilizer containing 17% urea and 83%
water
46.8 - " - sulphuric acid, 80 %, and
- " - water
are mixed. 100 parts by volume of a solution is obtained, the
flash point of which is above 70C and which keeps at least one
month at -20C without forming a precipitate.
Example 2
31.0 parts by vol. of formalin, flash point 68C containing
q 37 % formaldehyde and 8.9 % methanol,
10.0 - " - stabilizer containing 17 % urea and 83 %
water,
- 3 -
' ' '
1075075
37.4 parts by vol. of sulphuric acid, 80 %, and
26.1 - " - water
are mixed. 100 parts by volume of a solution is obtained, the
flash point of which is 70C and which keeps at least one month
at -20C without forming a precipitate.
Example 3
31 parts by vol. of formalin, flash point 68C containing 37 %
formaldehyde and 8.9 % methanol,
10 - l' - stabilizer containing 17 % urea and 83 %
water,
42.1 - " - sulphuric acid, 80 %, and
20.9 - ~ - water
are mixed. 100 parts by volume of a solution is obtained the flash
point of which is 70C and which keeps at least one month at -20C
without forming a precipitate.
Example 4
18.6 parts by vol. of formalin containing 37 % formaldehyde
and 4.5 % methanol,
46.8 - " - sulphuric acid, 80 %,
~ " - stabilizer containing 17 % urea and 83 %
water~ and
29.5 ~ " - water
are mixed. 100 parts by volume of a solution is obtained the flash
point of which is above 70C and which keeps at least one month
at -20C without forming a precipitate.
Because concentrated, 80%, sulphuric acid is used in the examples,
the volume of the obtained solution does not correspond to the sum
of the amounts of the different substances.
Example 5
31.0 parts by vol. of formalin containing 40 % formaldehyde,
37.8 - " - phosphoric acid, 85%,
10.0 , " - stabilizer, and
21.2 - ~' - water
are mixed. The flash point of the solution obtained is above 70C
and it keeps at -20C without forming a precipitate.
.
- 4 -
iO75075
Example 6
21.4 parts by vol. of formalin containing 35.2 % for~aldehyde
and 6.3 % methanol,
60.0 - " - hydrochloric acid, 37%,
10.0 - " - stabilizer~ and
9.6 - " - water
are mixed. A clear solution is obtained the flash point of which
after storing for 10 months is 65C and which keeps at -20C 10
months without precipitating.
The water content may also be substituted with acid.
.
;'' . ,' . : , : `
6 1075075
~ oO
h ~3 + III++ .+;.
~ U N I I I I + + +
~ol ~b
N
N I I I I ~ + +
01 1
Q~
J~ ~0
~ .~ ~ +
4~ U
~ oo
rl C~ N I I I I + + +
U~ I
_l . ~
~ ~ &J ~
.C ra ~ N
~_ +
- 0 tl) O
~ C) O
O dP ~ O l l l l l l l ~
U l ~1
<~ ~ . O
U~ U~ U~
O ~: ~ l l l l l l I h
t` + . C)
a 3-,1 ,~
~ ~I bO - U
H ~ O~1 ~ h ,_
u~ a ~ a~ u~ ~3
~3 ~ i~
O b3 ~ U ~_' Q)
,~ ~ . Q) d C~ ~: h :i o
~d ~ ,1 ra ~ H 4 ~ ~D ~ t` C.) ~
rd ~; U _~ ~ ~ O ~a
N h~ n~ rl ~ ~ ~_ co ,1
,~ rd h ~; b3 ~D ,~
3 ' ~ rl o o~ Q .~ . ..
,4 h (:: ~ h P ~4 ~? ,~
~ ~ ~ ~ to ~:
+~ Ul a5 11~ ~ ~- ~.--1 11
tq ~ ~ ~t~ o~~1
O ~ ~ ~ e +
~U -J ~ o ~ ~ o
rlC ~ ~ . .
hO~rl h JJ ~ ~ a~
11~ u~ 4~ U
U ~ ~ P~O r. t~ O ~~ ~~ o o ~ ~1
~ao o-,l ~1
C~1 ~( ~ ~Y~ ~
Q) O r~ O u
'1 0 L~ ,~J N O ~) N NO L~ ~ tD O
~0 :3P CP ~ L'~
O,4 ~ ~ 11
' '
~1 ~ ,_ -
'' ~ O O 0 ~ C~
a) o ~ a~ ~ ~ c~ U~ N ~0
o ~ o h ~ ~ ~ t~J ~ N ~
:~ ~
.~
Ll~ 0 .4 U ~ Il) ~I bll
.
1075075
~CO~ ~ ++ +~++
~o'
+
o ~ ~
+,, . . ++ ++++
~o'
N ~ +
00 ~ ++ ++++
Ul ~ _
ao~
O ~ +
rl C~l ~ + ++++
~0
b ~+~I ~ +
~
~ o
o o ~~ - - - - + + + + +
~n l
c o~ ~ +
o ~
V o ~ - - + + + + +
C ~ _
qo
~ ~ ~ ~ _, - .
U~ ~ N+ O
u ~ ~a -
O ~U
c C ~ 0~ . + + + e
C ,~ 0
Du . +
rl O D
.,1 1~ U ~1 ~ Ul C
u g ~~C ~ a~ N O :~O :~. a~
U~ ~U 3 U o~ ~Uc ~ ~ ,
~ C _ ~ ~ .~;
_1 ~U C ~ _ ~ ~:1
Ul OD 1: C ~o _.
~o C
C C oo ~ ~ o ~o ?~ ~0
~ ~ ~ ~ ~a~ ta ~
00 ta ~ C ta U c ,~ ~ ~
fn C ~' ' --I _I ~ O I~ I~
Q~ C ;~ 3 ¢~ _ _ ~
~1 U 1` ~ ~ Ul C ~` . C
O _ ~ ~ 00 O O O O O O O O O O O
U~ ~ ~ ~`-- ~ C C~ '.'
C 0 ~ ~_ O O
~1 0 N ~ U ~ U O
I~
_I u _ ,~ 3 O O -I Ir 0 a~ O O O U~ ~ ~o u~ -1 U
~a o ~D~ e N ~ t~) N N N ~ N a~ ~D N O _ C
. ~ Oe o
~1 ~ Il~ ~1 .~
cu~ o ~ c ~ ~ ~o 1` 0 a~ o ~ ) lo
O Di~ 0O ~ ~ u~ 0 _I ~ I` _I ~ I` O ~) ~D ~ n~
_~ _ _, ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ i~
~U ~ 0 ~ C
0 o
~4 EO~ ~ ~ 0 a~
U~
.
.
~.~
10~75075
From tables I and II can be seen that the solutions stay
clear for a long time within very narrow limits, according to
table I (where the formalin contains 8.9 % methanol), the ratio
of formalin : acid being 1 : 1.2 to 1 : 1.5 (b,c,d) and according
to table II (where the formalin contains only 4.8 % methanol) within
the limits formalin : acid 1 : 1.68 to l : 2.5 (2,3,4,5). The diffe-
rence is obviously due to the different methanol concentrations.
Within these limits the solutions have stayed clear for one month
at room temperature to -20C and the flash point has been 67C to
~70C
According to our experience a solution which stays clear for
one month will continue to stay unchanged.
Performed conserving tests have given extremely good results.
These results are given in the following examples.
Test 1
Composition of the Formic Test Viher- Press
test solutions acid solution solution fodder
(80 %)
Formalin vol.% 35 55
N2SO4 (80%) vol.% 44
Acetic acid -"- - 24
Water -"- 21 21
Contents of effluent
juice:
Dry matter (Z) 5.69 5.19 5.16 5.72
Protein (%) 1.66 1.35 1.31 1.80
Quality of silage:
pH 3.8 4.1 4.2 4.2
Raw protein (in dry
matter) 22.1 22.4 22.1 20.7
Digestible raw protein
g/fodder unit 183 192 190 181
In all experiments the preserving solution has been used at
an amount of 5 1/1000 ~g fodder.
- 8 -
`- 107507~
Thus it can be seen that in test solution 1 less dry
matter and protein escape from the silo together with the efflu-
ent juice than is the case with fodder preserved with formic acid.
On the other hand the corresponding values are more or
less the same both for the Viher-solution and the test solution 1,
although test solution 1 contained considerably less formalin
than the Viher-solution.
The following test concerned the amounts of CO2 formed,
which formation indicates impure fermentation in the fodder mass.
Test 2 -
Formic Test Viher-
acid solution solution
(80~)
Amount of CO2
g/1000 kg of 289 0 37
fodder
Test solution 1 gave also in this respect a better re-
sult than the other. The evolution of gas from the press fodder
was so great that it was not possible to collect it all.
Test 3
- 20 Composition of Formic Test Test Press
test solution acid solution solution fodder
(80%) 2 3
I Formalin vol. % 26 26
- H2SO4 (80%) vol. % 31 47
Water 43 27
Quality of fodder: -
pH 4.39 4.17 3.94 4.84
Lactic acid (%) 0.48 1.23 0.95 1.14
Acetic acid (%) 0.21 0.47 0.29 0.74
; Propionic acid (%) 0.09 0.06 0.06 0.10
Soluble N % of tot.N 50.4 46.2 39.9 57.7 --
Content of protein
in effluent juice % 1.48 1.36 1.34 1.64
.. ''' ' '
:~07S075
The amount of preserving solution used in all tests is 5
1/1000 kg of fodder.
The amount of preserving solution per 1000 kg, used in
the preceding examples, may of course vary to some extent, depend-
ing on the quality of the fodder as well as Oh other conditions.
A suitable amount is generally 4-6 1/1000 kg fodder. -
From the results is seen that the acid addition has a
pH lowering effect. In the test/preserving solution was used to
give an acid amount per 1000 kg fodder as follows:
Formic acid 80 equiv.
Test solution 2 44 "
Test solution 3 66 "
More effective than the acid addi'ion is, however, the
combined effect of formalin and acid when used at the above ratios.
The formation of the desired acids has been most effec-
tive in a preserving solution having a formalin : acid ratio of
1 : 1.2 (test solution 2). Even stronger has been the formation
of acid in press fodder, but its pH has not however decreased to
the desired level.
Test 4
Composition of the Test Test Test Formic
test solutions: Solution Solution Solution acid (80%)
4 5 6
-
Hydrochloric acid
35% 72 vol% 39 vol%14 vol%
Formalin 2B " 61 " 86 "
Formalin:Hydro-
chloric acid 1:2.57 1:0.64 1:0.16
; added amount 1/1000 kg 6.0 5.7 8.1 4.0
Acid equiv./1000 kg
' fodder 49.5 26.0 13.0 90.0
; 30 Conserving results
pH 4.45 4.75 4.92 4.41
Lactic acid (%) 0.88 0.76 0.54 0.61
Soluble N/tot.N (%) 33.5 29.0 25.6 46.6
-- 10 --
1075075
(Test 4 cont)
Conserving losses:
Dry matter (%) 0.2 3.3 6.1 5.2
Ash (%) 5.5 15.5 18.9 7.2
Raw protein (%) 1.7 2.7 8.8 6.5
Fibres (%) 7.6 16.8 15.2 10.4
Palatableness for
sheep:
g dry matter/day/sheep 1035 1068 772 1007
The test resuLts show that the best conserving results were
obtained with a combination, in which the ratio of formalin to
hydrochloric acid was about 1:2.5. With this combination the
same pH-level in fodder was reached as by using formic acid, the acid
effect of which is about twice to that of test solution 4.
When formalin and acid are used in the above ratio, the sub- - -
stances increase the effect of each other. In this way a good
conserving effect is obtained with only small losses.
Test 5 - -
Composition of Test Viher- Press
test solutions solution solution fodder
Formalin vol% 21 55
H2S04 (80%) 47 _-
Acetic acid 24
Quality of fodder:
pH 4.2 5.1 5.3
NH4-N (%) 0.024 0.028 0.071
Pure protein (%) 2.7 2.8 1.5
Sugar (%) 0.6 1.6 0.2
Lactic acid (%) 3.0 2.1 1.5
Palatableness:
kg/beef cattle/day 26.5 25.2 21.5
Digestible raw protein
g/fodder unit 202 211 178
,
- 11 -
1075075
Test solution 7 has brought forth a strong formation of
lactic acid~ which together with the added acid has remarkably
decreased the pH. The smaller amount of acid and the greater
amount of formalin in the Viher-solution have slowed down the
lactic acid fermentation. The smaller amount of formalin inttest
solution 7 has been sufficient to protect the fodder against
protein losses.
- 12 -
.
1 3 10750'75
~o ,~ _
C~J +
o~, _ _
~o ,_ ~ _
l l l l
~ _ ~
oc~
~o ~_~ _
,~ l l l l
o ~ ~
C`J
. o C) +
Q~ . .,
,` ~ O ~ U)ON .
h ._. ~ I .
:. G)
a) o~
C~ N .
~ + I I .1
~ 3
a~ o ~ ,c ~ ~ _
. . ~ U~
h N ~ ~ ~ ,1
- O ,~;, r` ~ .~ .
0~ o U~ .;
O :tODC~I
N ~ O ~ : O
,~ 1 ~
'-~ O'~ h tn
. - c~ ~ Q ~1
U~ ~1 r1 ~ ~
O t~ ~ r~
~ ~ O t~ 3 C~ . . . .
U
- :
. .
'~'
';
1075075
Table IV
Palatableness: Press Viher-solution Viher-acidX) Propionic +
fodder (acc.to Finnish sulphuric acid
pat.43941)
kg/animal/day 18.2 19.7 21.0 18.6
growth increase
kg 69.3 84.6 102.0 83.5
-"- g/day 598 730 879 720
Viher-acid contains:
Sulphuric acid H2S04 42.0 /O
Formalin , 40 % HCH0 25.0 %
Urea (NH2)2C0 1.7 %
Water H20 31.3 %
It has thus been proved that the preserving solutions meet
the extremely high demands of stabilization and fodder conservation.
_ 14 -
