IE43977B1 - Stavilized fodder preserving solution containing formaldehyde - Google Patents

Abstract

1518808 Fodder preservative FARMOS OY 9 Dec 1975 [17 Dec 1974] 50356/75 Heading A2D A stabilised fodder preserving solution contains formaldehyde (added as a formalin solution), an organic acid and or an inorganic acid and urea as a stabiliser, the volume ratio of the formalin and acid being within the range 1 : 1.2 to 1 : 2.5, the solution containing 8.5 to 13.5 acid equivalents per liter of solution and about 1 to 2% by weight of urea. The inorganic acid may be sulphuric acid. The organic acid may be formic or acetic acid.

Description

It is a well-known fact that formalin combined with other substances can be used as a fodder preserving agent. The advantageous effect of formalin on the conservation of fodder and the improving effect on the nutrient utilization are well-known facts, too. The problems have been the polymerization of formaldehyde in solutions, although formalin often contains for instance methanol as a polymerization inhibitor, and also the low flash point, above all in solutions where inorganic acids have been used, such as sulphuric 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 generally been rather small, only about 3 to 5 acid equivalents (grammes of acid corresponding to its equivalent weight) per liter. 42377 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 large pH decrease toget er 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 advantage that the cost of the product will decrease correspondingly.

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 0y)), which is described in Finnish Patent No. 43913, (British Patent No. 1,276,671), and Sylade (Imperial Chemical Industries), which is described in the Finnish Patent Application No. 3276/72, (Patent Specification No. '36978), according to which even 9 parts by volume of formalin to one part by 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 diminishing, so 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 comparatively narrow limits which limits also in preservation experiments have proved considerably more advantageous than those prior used.

The invention concerns stabilizing fodder preserving solutions containing formaldehyde, the characteristics of which appear from the appended claims. The stabilized solutions comprise formalin and an inorganic and/or organic acid. The preferred inorganic acids are hydrochloric, sulphuric and/or phosphoric acid and the preferred organic acid is formic acid. The preserving solution has both a good conserving and stabilizing effect when the formalin : acid ratio is 1:1.2 to 1:2.5 by volume whereby the solution contains 8.5 to 13.5 equivalents of acid per liter solution.

By formalin is meant a 35 to 40% aqueous formaldehyde solution 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, urea, e.g. in an amount of about 1 to 2 percent by weight 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 -20°C) the flash point at the same time staying sufficiently high.

According to the Finnish Statute No. 335/54 concerning flammable liquids, a liquid, the flash point of which is below 55°C, is considerrd 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. Ζ Λ C «7 ·7 hi 4* 4 i To the aboye 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 problems in a way that is rather suiprising 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 percent by weight if not otherwise indicated.

Example 1 10 27.9 parts by volume of formalin, which contains 37% formaldehyde and 4.8% methanol, parts by volume of stabilizer containing 17% urea and 83% water 46.8 parts by volume of sulphuric acid, 80%, and 10 parts by volume of water are mixed. 100 parts by volume of a solution is obtained, the flash point of which is above 70°C and which keeps at least one month at -20°C without forming a precipitate.

Example 2 31.0 parts by volume of formalin, flash point 68°C containing 37% formaldehyde and 8.9% methanol, .0 parts by volume of stabilizer containing 17% urea and 83% water, 37.4 parts by volume of sulphuric acid, 80%, and 26.1 parts by volume of water 3077 are mixed. 100 parts by volume of a solution is obtained, the flash point of which is 70°C and which keeps at least one month at -20°C without forming a precipitate.

Example 3 31 parts by volume of formalin, flash point 68°C, containing 37% formaldehyde and 8.9% methanol, parts by volume of stabilizer containing 17% urea and 63% water, 42.1 parts by volume of sulphuric acid, 80%, and .9 parts by volume of water are mixed. 100 parts by volume of a solution is obtained, the flash point of which is 70°C and which keeps at least one month at -20°C without forming a precipitate.

Example 4 !0 18.6 parts by 46.8 parts by 10 parts by 29.5 parts by are mixed. 100 of which is above without forming a volume of formalin containing 37% formaldehyde and 4.5% methanol, volume of sulphuric acid, 80%, volume of stabilizer containing 17% urea, and 83% water, and volume water parts by volume of a solution is obtained the flash point 70°C and which keeps at least one month at -20°C precipitate. · i .

** *· «J * Because concentrated, 30%, 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 volume of formalin containing 40% formaldehyde, 37.8 parts by volume of phosphoric acid, 8b%, .0 parts by volume of stabilizer (as in Examples 1-4), and 21.2 parts by volume of water are mixed. The flash point of the solution obtained is above 70°C 10 and it keeps at -20°C without forming a precipitate.

Example 6 21.4 parts by volume of formalin containing 35.2% formaldehyde and 6.3% methanol, 60.0 parts by volume of hydrochloric acid, 37%, .0 parts by volume of stabilizer (as in Examples 1-5), and 9.6 parts by volume of water are mixed. A clear solution is obtained, the flash point of which after storing for 10 months is 65°C and which keeps at -20°C ten months without precipitating. η> Έ o o E CM CM -ί- Τ' I 1 -f- + + Ο «Λ Ο >5 CM 1 1 1 + + + rd r to o CO CM t—· CM 1 1 1 1 1 1 + O Φ w © 4J >j CM | 1 1 + + + rd rd 1 4-5 TO •r- O CL Tt CM •i- r— CM | i 1 1 1 a + φ E ' a. wo >> © id CM 1 I 1 + + + TO 1 r— O i— CM CM 1 1 1 1 I 1 + w o >> o 1 | 1 1 1 1 το ι Γ”- o CM CM 1 1 1 1 1 1 + 5- w, ιυ Φ >> w >.C N rd >> Ο Ρ Φ TO rd Ο Φ O TO x-s. *-* c e CO Tt Ps. r— r— 4- r—' Ο C Φ (0 |— -Ε JO Ρ P Φ P c cn ε •r- C Φ Ο Τ- W «*“S. 3-5 j= Ο. > >> w © 4-3 E ra >> J= Ε φ TO ra co E WOW TO Ε •Ι- <0 4-5 E sp tp O ΤΟ φ r— 4- O CO r— ps. «t Ε 4-5 Ε Lu rd O <Ο rd Φ 3 > Φ 3¾ © ΤΟ CO >» 00 το JE P _Ε •t— W C -~s Φ TO υ id ·!- O Ό c rd r- O O ps. ps. O o o © © γ— rd LU CL >-* co co r*s Γ. ps. ps. P’s (0 υ ε Ε <0 ε A A A A ο Φ 3 ✓—s 4- s_ _c 3A 3 Q. 3« r— • P’s. 3¾ 3 O r— r- r—» cn CO tn co © co P-. W CM O • « t—· OC > o CO o in r~ co o 4- »_* co CM CM Γ” Ε O •ρ- Er_ Φ w (β N P ε •p- c X—X Ε 3 3¾ ο •r- Q Μ- JO ε Φ rd rd ε Μ~ P 3 Ο w Φ O 3¾ (— -C tn ο o CO r—. co in CM co 3¾ 3¾ P Ό-03 > « • χ s-z CM r>- CM CO CO o Φ Φ TO CO «ί Tt in in co ε ε Φ 3 3 to 1- r— TO c Ο O rd O > > Φ Ρ © E 3 CO rd O ra -Q U TO φ 4- © cn o m o ΙΛ i-4 r-4 CM Ο % CO .c W <Ό 4ο r— Ο w (Ο φ υ II Ρ II υ φ ε £2_ I I + + + + 077 X= O P CJ C I ω >5 O <0 o XJ CJ I σ» o I— CJ CJ r— O r— CJ CJ + o ω o S cj + + + + + + ii ι ι i + + + + + + + ι ι ι ι ι + I + + + + + » ΓΊ S; tr (Λ Ρ ω α> ρ c Φ iφ Ρ Ρ Ρ χ: cn Fx CJ CJ + V O ω CJ >> 1 ro XJ o CJ ter CJ + o <Λ © >, CJ ro 1 Ό o CJ CJ CJ + o >3 o ro CJ XJ 1 o c ro c P Φ E XJ c ro c r— <ο Χ5 ro ρ fO φ Φ ί. χ: Ρ •γ- φ <-χ cn > 5 W u Ο C ω cn >j co -rm c -Q χ-* ι— nS P c o u •I- T- Cl Φ XJ >> φ Φ N Ο P QJ Ο Φ X-^C i•i— p x: p s- Φ V) C Φ M ro ♦!“ P C r— Ο Ρ O Lu CL «3 U ΧΞ P V) C ·—«· ro ·«- υ <— oo LlCL^ o o CJ > X ι c s* S- T- . O r~ <— Ll- (Ο O ε > (Λ >> ro O X? tx A >» ro Ο Ό fX A H. Αχ-* ro © XJ Γχ Cx ω >» ro o x> rx o rx o Γχ © rx o ιχ o rx © rx O ιχ © rx © rx © rx o rx A A Λ A A A A A A A A γ- to co © © o o LO *+ © LO γο CQ cn CJ to CJ CJ CJ © r LO 1— CJ r— © LO CJ ό LO LO rx ra © o r— CJ CQ *r LO LQ CO r— ro- rx i— rx ό CQ © CJ CJ CJ ro CQ CQ «sr eT ro- CJ CQ LO LO IX CO © O m rI rx CQ Φ ro χ: γη· Ll.

O CM 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 th Table II (where the formalin contains only 4.8% methanol) within the limits formalin : acid 1 : 1.68 to 1 : 2.5 (2, 3, 4, 5). The difference is obviously due to the different methanol concentrations. Within these limits the solutions have stayed clear for one month at room temperature to -20°C and the flash point has been 67°C to >70°C.

According to our experience a solution which stays clear for one month will continue to stay unchanged.

Performing conserving tests have given extremely good results. These results are given in the following examples. 4D077 Test Ί Composition of the test solutions Formi c acid (80%) Test solution 1 Vi hersolution Press fodder Formalin vol.% 35 55 H2S04 (80%) vol. % 44 - Acetic acid vol. % - 24 Water vol. % 21 21 Contents of effluent juice: Dry matter (%) 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 T81 In all experiments the preserving solution has been used at an amount of 1/1000 kg. fodder.

Thus it can be seen that in test solution 1 less dry matter and protein escape from the silo together with the effluent 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 C02 formed, which formation indicates impure fermentation in the fodder mass.

Test 2 Formic acid (80%) Test Vihersolution solution Amount of C02 g/1000 kg of fodder 289 0 Test solution 1 gave also in this respect a better result than the other. The evolution of gas from the press fodder was so great that it was not possible to collect it all. /' Γ» Λ r» r * to ϋ I 7 Test 3 Composition of test solution Formic acid (80%) Test solution 2 Test solution 3 Press fodder Formalin vol.% 26 26 H2S04 (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 The amount of preserving solution used in ail 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, depending on the quality of the fodder as well as on 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 1000kg. fodder as follows: Formic acid equiv.

Test solution 2 44 11 Test solution 3 66 More effective than the acid addition is, however, the combined effect of formalin and acid when used at the above ratios.

The formation of the desired acids has been most effective 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 Compositions of the Test Test Test Formic acid test solutions: solution 4 solution 5 solution 6 (80%) Hydrochloric acid 35% 72 vol. % 39 vol.% 14 vol.% Formalin 28 61 86 Formalin:hydrochloric acid 1:2.57 1:0.64 1:0.16 added amount l/1000kg 6.0 5.7 8.1 4.0 Acid equiv./1000 kg fodder 49.5 26.0 13.0 90.0 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 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 42077 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-l'-vel in fodder was reached as by using formic aicd, the acid effect-of which is about twice tn that of test solution 4.

When formalin and acid are used in the above ratio, the substances increase the effect of each other. In this way a good conserving effect is obtained with only small losses. ,1 Ο ** Test 5 Composition of test solutions Test solution 7 Viher- solution Press 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 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 in test solution 7 has been sufficient to protect the fodder against protein losses. ω ο j= ο P CM C OJ O I 4Ξ977 LO • o r- O f— OJ OJ + till TABLE III o o OJ ΙΛ CM Φ _c ι P P nj c P o cj •ί- ε © Ο. OJ LO 0J u + Φ t- C r~- CL ο O c CJ Ρ nJ o 3 x: 0J (“ P OJ ο φ ω ι ΙΛ ε >» (0 σ> XJ CJ C co o CO 0J > ,—- «3· 0J J- S- + φ Φ ω Ρ φ (0 Φ (Λ ί- 3 ~σ x: ο. 55 P _c c φ co Φ o _c co XJ ε w Ρ Ρ nj LO ω <4- ft ε • φ Ο nJ &. r“ Ρ Φ o r— >> t_ <4- c Ρ 3 ο •ι— S3 ti >* r“ U S3 OJ C r— Ρ Π3 • ‘I- φ <0 γ— LO O P Ν U s»/ CO CL nJ 1 —' (A •f— ι— •σ S- 3 JC XJ C cn Φ O ω φ J0 Π3 Ε N E r- ro ε ίθ •r— •r* i— r*“ ε Ρ Ρ C r— r- O Ll -ί- (/) C •r- «ο Μ- <0 _Q ε Ο Ρ nJ s- ω Ο- c P O nJ Ο Ο to M- OJ ΧΙ ο XJ X (Λ qj φ «r- (β C ε ε υ Γ-“ ο 3 3 nJ Lu (Λ Ρ O o o P 3 > > T- ur_ ε Π3 Ο 25 >> £ CL ιη X» -Q O X P O U W (Λ 1— •Γ P Ρ Ό CJ Q O ΙΛ S- S- OJ XCO > «3 <0 «3 XJ J0 cl CL XJ Π3 Π3 o CO «Λ c Ο Π3 o Η- 1 ι 3 P 3 o to o LA r—1 iiii to co CM OJ cn p >> Q. •r* υ φ 42977 Table IV Palatableness: . Press Viher-solution Viher-acidx) Propionic + fodder sulphuric acid kg/animal/day 18.2 19.7 21.0 18.0 growth increase kg 69.3 84.6 102.0 83.5 growth increase g/day 598 730 879 720 x) Viher-acid contains: Sulphuric acid HgSO^ 42.0% Formalin, 40% HCHO 25.0% Urea (NH2)2 CO 1.7% Water H,0 31.3% It has thus been proved that the preserving solutions meet the L5 extremely high demands of stabilization and fodder conservation.

Claims (8)

1. A stabilized fodder preserving solution containing formaldehyde and an organic acid and/or inorganic acid and urea as a stabilizer, characterized in that the volume ratio of the formaldehyde expressed 5 as 35 to 40% fo-malin and the acid used falls within the range 1:1.2 to 1:2.5, the solution containing 8.5 io 13.5 acid equivalents per liter of solution.

2. A preserving solution accordin': to claim 1, wherein the solution contains methanol. 10

3. A preserving solution according to claim 1, including as inorganic acid 80% sulphuric acid.

4. A preserving solution according to claim 1, including as inorganic acid 35% hydrochloric acid.

5. A preserving solution according to any preceding claim including 15 as organic acid 80% formic acid.

6. A preserving solution according to claim 1 or claim 5, including as inorganic acid 85% phosphoric acid (calculated as a dibasic acid).

7. A preserving solution according to any preceding claim containing 1 to 2% by weight of urea. 20

8. A stabilized fodder preserving solution according to claim 1 substantially as described herein with reference to any one of the Examples.