DE2555558A1 - FORMALDEHYDE CONTAINING STABILIZED PRESERVATIVE SOLUTION FOR FEED - Google Patents

Description

Stabilized preservation solution containing formaldehyde

for feed

As is well known, formalin can be used as a feed preservative in combination with other substances. Also the reduction losses in preservation due to formalin and the improvement in nutrient utilization due to formalin are known. The problems encountered with its use were the polymerization of formaldehyde in solutions, although formalin often contains, for example, methanol as a polymerization inhibitor, and the low flash point, especially in solutions, in which inorganic acids, such as sulfuric acid, hydrochloric acid and phosphoric acid can be used.

A well-known and experimentally proven method is to take the formalin and the acid from separate containers in individually set relationship only in the stage of manufacture

609826/0701

Place the preserved feed directly into the feed using its own mixing device.

However, this has been the case, mainly because of the polymerization of formaldehyde and the difficulty in handling the strong Acids, proved to be an unsuitable method in practice. In addition, when using formalin and acid together in the same solution gives a better result than if each of these substances is used on its own.

The amount of acid in the formalin in question Preservation solutions were quite low, that is, on the order of only about "3 to 5 acid equivalents each Liter.

In order to achieve a better preservative effect, it would be useful to increase the amount of acid so that the pH of the feed is more likely to decrease.

Recent studies have shown that a relatively strong decrease in pH is combined with the preservative effect formaldehyde leads to the best possible result in terms of feed preservation. If the acid used, for example Is hydrochloric acid or sulfuric acid, increasing the amount of acid has the further advantage that the cost of the product is increased become correspondingly lower.

Furthermore, those currently used for feed preservation contain Formalin-containing solutions predominantly formalin, for example in a ratio of 1 part acid to 2 parts Formalin (so-called Viher solution [Farmos Oy]), as described in Finnish patent 4.39 ^ 1, and according to Sylade (Imperial

609826/0701

_ "5 -

Chemical Industries), described in the Finnish patent application 3276/72, according to which even 9 parts by volume of formalin per part by volume Acid can be used.

Unexpectedly it has now been found that the proportion of formalin in the preservation solution can be reduced considerably, without reducing the beneficial preservative effect of formalin with regard to feed quality and nutrient preservation will.

At the same time, laboratory tests have surprisingly shown that the preservative solutions containing formalin can be prepared so that they remain clear when the ratio Formalin and acid are kept within relatively narrow limits, these limits also being used in conservation experiments proved to be considerably more beneficial than the ratios used previously.

The invention relates to a stabilized one containing formalin Feed preservation solution according to patent claims. The stabilized solution contains formalin and inorganic or organic Acid, the inorganic acids being hydrochloric acid, sulfuric acid and / or phosphoric acid and the organic acid being formic acid or mixtures of these acids come into question. The limits within which the preservation solution is both good preservative as well as stabilizing effect are formalin: acid = 1: 1.2 to 1: 2.5, based on the volume, with the solution Contains 8.5 to 13.5 equivalents of acid, ie liters of solution.

Formalin is a 35% aqueous formaldehyde solution, which contains methanol and which also contains, for example, carboxymethyl cellulose, Hydro xyä thy lee Hu lose, vinyl acetate telomer or

609826/0701

another known formaldehyde stabilizer has been added, to understand.

Regardless of the formalin initially added stabilizing agents of the preservation solution according to the invention are about 1 to 2 wt -.% Urea, preferably dissolved in water before mixing, is added.

Stabilization means that the solution can be used within a wide temperature range (from room temperature to -20'C) remains clear while at the same time the flash point remains sufficiently high.

According to Statute No. "335/5 ^ · concerning flammable liquids, a liquid with a flash point below 55 ^e C is to be regarded as belonging to the group of flammable liquids. With the stabilized preservative according to the invention, not only is polymerization prevented, but also sufficient high flash point guaranteed.

Regarding the stabilization problem mentioned above, chemists have been looking for a simple, economical and Looking for a practical solution, but so far without success. With the preservation solution according to the invention, this problem is now been solved in a manner surprising even to the person skilled in the art.

The following examples and tables illustrate the invention regarding the stabilization of the solutions. Figures in percent relate to weight, unless otherwise stated.

609826/070 1

example 1

27.9 parts by volume of formalin, the 37 $ formaldehyde and 4.8 $ methanol

contain,
10 parts by volume of stabilizer, of $ 17 urea and $ 83 water

contains,

46.8 parts by volume of sulfuric acid, 80 $, and 10 parts by volume of water

are mixed together. To obtain 100 parts by volume of a solution having a flash point greater than 70 ⁰ C, which is durable at least one month at -20 ⁰ C without forming a precipitate.

Example 2

31.0 parts by volume of formalin, flash point 68 "C, with a content of

37 $ formaldehyde and 8.9 $ methanol,

10.0 parts by volume stabilizer with a content of 17 $ urea

and $ 83 water, 37.4 parts by volume sulfuric acid, $ 80, and

26.1 Parts by volume of water

are mixed together. 100 parts by volume of a solution with a flash point of 70 ° C. are obtained, which last for at least one month is stable at -20 * C without forming a precipitate.

Example 3

31 parts by volume of formalin, flash point 68'C, with a content of

37 $ formaldehyde and 8.9 $ methanol,

10 parts by volume of stabilizer, of $ 17 urea and $ 83 water

contains,

42.1 parts by volume of sulfuric acid, 80 $, and

20.9 parts by volume of water

are mixed together. To obtain 100 parts by volume of a solution having a flash point of 70 ^e C, which is durable at least one month at -20 C ^8, without forming a precipitate.

6 09826/0701

Example 4

18.6 parts by volume of formalin, 57 $ formaldehyde and 4.5 $ methanol

contains,

46.8 parts by volume of sulfuric acid, BO $ -ig, 10 parts by volume of stabilizer, of $ 17 urea and $ 83 water

contains, and 29.5 parts by volume V / ater

are mixed together. Mari receives 100 parts by volume of a solution with a flash point above 70 ⁰ C, which can be kept for at least one month at -20 ⁶ C without forming a precipitate.

Concentrated sulfuric acid used in the examples the volume of the solution obtained does not correspond to the sum of the amounts of the various substances.

Example 5

.31.0 parts by volume of formalin with a content of 4-0 $ formaldehyde, 37 »8 parts by volume of phosphoric acid, 85 $,
10.0 parts by volume of stabilizer and
21.2 parts by volume of water

are mixed together. The flash point of the solution obtained is above 70 ^° C. and the solution remains at -20 ° C. without forming a precipitate.

Example 6

21.4 parts by volume of formalin with a content of 35 * 2 $ formaldehyde

and $ 6.3 methanol, 6o, 0 parts by volume of hydrochloric acid, $ 37, 10.0 parts by volume of stabilizer and

9.6 parts by volume of water
are mixed together. A clear solution is obtained, whose

609826/070 1

-η -

The flash point after 1ü-month storage is 6 ^ ⁸ C and which lasts 10 months at -20'C without forming a precipitate.

The water contained can also be replaced by acid.

609826/0701

Table I. Stabilization tests

Flash point and clarity of preservation solutions containing different amounts of sulfuric acid contain

The initial solution, the

31 volume $ formalin (37 $ formaldehyde and 8.9 $ methanol) and

10 volume $ stabilizer (17 $ urea and 83 $ water)

contains, the amounts of sulfuric acid given in the table are added.

00

H ₂ SO ₄ ,

H ₂ O,

^Solutions ($ 8o) Volume- $ Volume-5

Flash point, point

, «After d.

⁰ preservation, ⁰ C

In the rain

freeze 7 days 11 days 14 days 18 days 1 Mcnat

^ O ti T * 3 7 * 1 II!

+ 22 ° -20 ° + 22 ° -20 ° + 22 ° -20 ° + 22 ° -20 ° + 22 ° -20 °

32.8 30.7 67 64

(14 days) (14 days)

b 37.4 26.1 67 70 70 C. 42.1 20.9 70 (14 days) (14 days) π 46.8 15.8 > 70 e 51.5 11.5 > 70 f 56.2 6.8 > 70 60.8 0.9 > 70

cn cn cn _cn co

Flash point of formalin: 68 ¹ C

+ = Precipitation, (+) = cloudy, - = clear 'solution

Table II Stabilization tests

Flash point and clarity of preservation solutions containing various amounts of formalin

The starting solution, the 10 volume $ stabilizer (17 lbs urea and 83 $ water)

Contains 46.8% sulfuric acid (80% by volume), the amounts of formalin given in the table are added.

LQ- ' Forma- H ^ O, Flamm- Flamm- Im Ge

Days 4 days 7 days 11 days 19 days 1 month

Vol-Ji Vol-J6

1 day
sung lin, ^fc dot, dot freeze- ~ _o ο ο οο 00

⁰ C after d. cabinet, + 22 ° -20 + 22-20 + 22-20 +22 -20 '+22' Conser- "C
four,

15.5

18.6 21.7 24, ö 27.9 31.0 34.1

37.2 40.3 43.3 46.5

33.1

29.5 25.8

22.9 19.0 15.0 12.0

9.5 6.4 2.6 0.5

> 70

>> 70

> 70> 70

>

> 70> 70> 70> 70

> 70> 70 (7 days) (7 days

> 70> 70 (7 days) (7 days

Λ-

The formalin contains 37 $ formaldehyde and 4.8 $ methanol.
Flash point 70 »C

It can be seen from Tables J and TI that the solutions remain clear for a long time if the ratios are kept within narrow limits, according to T ^r bel! · C (the formalin containing 8.9% methanol) Formal in: acid 1: 1.2 to 1: 1.5 (b, c, d) and according to Table TT (according to which the formalin contains only k, li'jC methanol) Formalin: acid 1: 1.68 to 1: 2.5 (2,. ' 5,4,5), the difference is obviously due to the different methanol concentration. Within these limits, the solutions remained for one month at room temperature to -2 (K: stable, and the flash point was 6'f to>7'0 ^B ".

Experience has shown that a solution lasts for a month remains, remains unchanged.

The preservation tests carried out have been extraordinary shown good results. These outlines are in the following Examples are shared.

Test 1

Composition of the test solution

Ant test solution (Soy-ig) solution 1

Viher press solution forage

Formalin, volum-fi

Acetic acid, volume $ water, YoLuin-fu

Content of the draining juice:

Dry matter, % 5.69 protein, % 1.66

Quality of the silage: pH 5, ο

Crude protein (in the dry material)

22.1

Digestible crude protein g / feed unit

21

22.4

92

55

24
21

5, 19th 5, 1ö 5, 72 1, 55 1, 51 1, 80

4.2

190

22.1 20.7

131

6 0 9 8 2 6/0701

ORfQINAl INSPECTED

In all experiments, the preservation solution was used in an amount used by 5 1/1000 kg putters.

It can be seen from the above values that when using the test solution 1 less dry material and protein can escape from the silo together with the draining juice than with one with Formic acid preserved feed.

On the other hand, the corresponding values are for the Viher solution and test solution 1 more or less the same, although the test solution contained considerably less formalin than the Viher solution.

The following test concerns the amount of COp that is formed indicates an impure fermentation of the feed mass.

Test 2

Ant test solution Vihersäure (8o # -ig) solution

Amount of COp

g / 1000 kg feed 289 0 37

Test solution 1 gave a better result than the other solution in this regard. The development of gas from the press chuck was like this strong that it could not be completely collected.

6 0 9 8 2 3/0701

Test 3

Composition
the test solution Formic acid
(805S-JJ ₅ ) Test solution
solution 2 Test solution
solution 3 Press
feed Formalin, vol- ^ 26th 26th H ₂ SO ^ (80 # -ig), volume 31 47 water 43 27 Quality of the feed: 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, % des
Total nitrogen 50.4 46.2 39.9 57.7 Protein content in
draining juice 1.48 1.36 1.34 1.64

In all tests, the preservation solution was used in an amount of 5 1/1000 kg of feed used.

The amount of preservation solution used in the previous examples per 1000 kg can of course to some extent depending on the quality of the feed as well as other conditions vary. A suitable amount is generally 4 to 6 1/1000 kg of feed.

The above results show that the addition of acid lowers the pH. In the test, the preservation solution was used in such a way that that the following amount of acid resulted per 1000 kg of feed:

Formic acid test solution 2 test solution 3

8o equivalents 44 " 66 "

609826/070 1

More effective than the acid addition, however, is the combined one Effect of formalin and acid when in the above proportions can be used.

The formation of the desired acids was extremely effective in one Preservation solution with a formalin: acid ratio of 1: 1.2 (test solution 2). The formation of acid in the press lining was even more effective, but its pH did / did not drop to the desired level Value.

Test 4

Composition of
Test solutions Test solution
solution 4 Test solution
solution 5 Test solution
solution 6 Ant sow
re (80? ü-i, ";) i 4.0 $ 35 hydrochloric acid 72 vol .- # 39 vol. & 14 vol. 90.0 Formalin 28 " 61 " 86 " 4.41 Formalin: hydrochloric acid 1: 2.57 \: 0.6k 1: 0.16 0.61 added amount
1/1000 kg 6, ο 5.7 8.1 46.6 Acid equivalent /
1000 kg feed " 49.5 26.0 13.0 Conservation
result, pH 4.45 4.75 4.92 5.2 Lactic acid, % 0.88 0.76 0.5 ¹ ^ 7.2 soluble N / total N, ^ 33.5 29.0 25.6 6.5 Preservation losses: 10.4 Dry matter, % 0.2 3.5 6.1 Ash, % 5.5 15.5 18.9 1007 Crude protein, % 1.7 2.7 8.8 Fiber material, % 7.6 1o, 8 15.2 Tasty i. ^ Iceit for
S chafe: g dry material / day /
sheep 1035 1 OdS 772

609826/0701

OR} GiMAL! NOPECTED

The test results show that the best preservation is with a combination in which the ratio of formalin to hydrochloric acid is about 1: 2.5 was achieved. With this combination, the same pH value was achieved in the putter as when using Formic acid, the acidic effect of which is about twice that of test solution 4.

When formalin and acid are used in the above ratio, the effect, leather of them will be increased. In this way, a good preservative effect is achieved with only low losses achieved.

Test 5

composition Test solution 7 Viher solution Chuck of the test solutions Formalin, vol- ^ 21 55 H ₂ SO ₄ (80 <-ig) 47 - acetic acid 24 Quality of the feed: PH 4.2 5.1 5.3 NH ^ -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 Palatability: kg / cattle / day 26.5 25.2 21.5 Digestible crude protein g / feed unit 202 211 178

The test solution 7 resulted in a strong formation of lactic acid, which together with the added acid the pH was lowered considerably.

60982 6/0701

The lower amount of acid and the greater amount of formalin in the Viher solution slowed lactic acid fermentation. "The smaller amount of formalin in the test solution 7 was sufficient to protect the food from a loss of protein z \ x.

60982 6/0 7 01

Table III Stabilization tests Flash point and clarity of the preservation solution

An initial solution that

10 parts by volume of stabilizer ($ 17 urea, $ 83 water)
31 parts by volume of formalin (35.2 $ formaldehyde, 4.3 $ methanol) °? contains, formic acid is added as follows:

fo · solution HCOOH HpO flash point precipitate

σι 8o $ -ig, initially 11.5 months 8 days 5 months 11.5 months

Parts by volume + 22'C -22 ^e C +22 »C -22 ^§ C +22 ⁶ C -22 ^e C

1 64.0 0 57 51 - (-) (-) +

2 57.6 6.4 63 44 _ _ - (_) (-)

3 51.2 12.8 65 63 ------

4 4s3 19.2 55 48 - - (-) (-). (-)

- ^clear K>

(-) somewhat cloudy ι cn

+ Precipitation ^ ₁

cn cn co

- 1T -

Table IV

palatability

Preßfutter Viher solution Viher-v \ (according to finrii acid ' see patent

kg / animal / day

Growth increase,

Growth increase, g / day 598

18.2 69.3

19.7
84.6
730

21.0
102.0
879

Propionic acid + sulfuric acid

18.6

83.5

720

Viher acid contains:

Sulfuric acid (HpS formalin, ko% HCHO urea [)
Water (H ₀ O)

42.0 %

25.0 %

1.7 %

31.3 %

It can thus be shown that the preservation solutions make high demands on stabilization and feed preservation suffice.

609826/0 7

Claims (7)

Claims A) Stabilized putter preservation solution that contains formaldehyde and organic acid, preferably formic acid, and / or inorganic acid, preferably sulfuric acid, hydrochloric acid or phosphoric acid, as well as urea stabilizer in addition to formaldehyde, characterized in that the volume ratio of 36- to 40 $ -igen formalin and the acid used is in the range from 1: 1.2 to 1: 2.5 and the solution contains 8.5 to 13 »5 equivalents of acid per liter of solution. 2. Preservation solution according to claim 1, characterized in that that the formalin in the solution contains methanol. 3. Preservation solution according to claim 1, characterized in that that the acid is 80% sulfuric acid. 4. Preservation solution according to claim 1, characterized in that that the acid is 35 ^ hydrochloric acid. 5. Preservation solution according to claim 1, characterized in that that the acid is 80 $ formic acid or an equivalent amount of acetic acid. 6. preservation solution according to claim 1, characterized in that the acid 85 ^ phosphoric acid, which is treated as dibasic acid in the preservation conditions. 609826/0701 7. preservation solution according to any one of claims 1 to '>, characterized in that it comprises about 10 $ Volum- of a urea solution of about 17 wt - contains.%. 609826/0701