FR2733425A1 - Rapid deodorisation of liq. animal excrement - Google Patents

Abstract

Rapid deodorisation of liq. manure comprises dissolving in the liq. manure, at least one soluble salt of an alkaline earth metal and at least one soluble salt of a metal of gps. VIII, IB or IIB.

Description

 The invention relates to a method for rapid deodorisaton slurry.

 On modern farms, animal droppings, feces and urine, as well as waste water or washing, are stored together and form what is called slurry. This practice is common for pigs, laying hens and cattle. Some large kennels also store dog droppings in this form.

 During storage, manure undergoes many chemical and biological transformations, one of the consequences of which is the formation of bad odors. The intensity and characteristics of these malodours vary according to the animal species and their diet. For example, pig manure is particularly complex, nauseating, pungent and persistent, causing serious odor nuisance in the vicinity, not only during storage in the farm, but especially during and after its application in the field.

 In the current state of knowledge, only the human being is able to say whether a product is fragrant or not, and to describe the types of odors ("noses" are still used in perfumery).

 Many products or processes have been proposed to suppress, or at least mitigate, manure odors.

 Extracts of Yucca schidigera are used in the feed to reduce the odor of pig faeces.

Alumina silicate (Klinofeed, Nutring ND, 35510 Cesson
Sévigné, France) is marketed as a food additive to reduce the odor nuisance of pig manure.

 E. NI. Barber and JB McQuitty (Can Agric., Eng., 1975, IZ, 90-96) teach us that sodium nitrate, NaNO3, or ammonium persulphate, (NH4) 2S208, or potassium permanganate, KNlnO4, can oxidize the sulfurized components and reduce the sulfur odor of pig manure after four days of incubation.

 Iron salts and metallic iron have been proposed to reduce the odor of pig manure. However, these products act only on hydrogen sulphide (SU2), which is only one of the many malodorous components of slurry (E M. Barber and JB McQuitty, Can Agric Agric., 1977, 12, 15 -19).

 A manure deodorization method called "oligolysis" uses the release, for a few days, of copper or iron metal ions, through two copper or iron electrodes connected to a continuous electric current.

 Japanese Patent JP 49 09 58 84 of 11.09.1974 teaches that a mixture of calcium cyanide, Ca (CN) 2, treated with oil, and containing 5-15% of FeSO4 and 5-15% of Activated charcoal can deodorize a poultry manure in five hours. The Nlerck Index (1989 Edition) states that calcium cyanide is a very toxic poison.

 JP NIolloy and H. Tunney (J. Agric., Res., 1983, 22, 37-45) teach us that ferric chloride, FeCl 3, 6H 2 O, aluminum chloride, AlCl 3, 6H 2 O, calcium chloride, CaCl2,6H2O, ferrous sulphate, FeSO4,7H2O, and magnesium chloride, 191gC12,6H2O, can decrease, each individually, the volatilization of ammonia during the drying of manure from pigs or cattle.

 All the products or processes mentioned have defects in their implementation to deodorize slurry: either too long (from 5 hours to a few days), or toxic (calcium cyanide), or only partially effective (only decrease a component bad odors, either hydrogen sulphide or ammonia).

 The invention therefore relates to a process for rapid deodorization of slurry, characterized in that at least one soluble salt of alkaline earth metal and at least one soluble salt of a metal of columns VIII, IB and IIB of the slurry is dissolved in slurry. the periodic classification of the elements.

 In particular, it has been discovered that non-toxic products, such as chlorides and / or calcium or magnesium sulphates, can, in the presence of soluble salts, such as chlorides and / or sulphates of metals such as iron, copper and zinc (belonging to columns VIII, IB and IlB, respectively), deodorize very quickly (in less than thirty minutes) and effectively slurry. The doses of each salt vary between 0.5 and 10 grams per liter of slurry, depending on the intensity of the smell of slurry and the desired level of deodorization.

 The following nonlimiting and non-exhaustive examples illustrate the invention.

EXAMPLE 1
500 ml of pig manure are introduced into each of the eight beakers of two liters volume.

 In the first beaker, the slurry is kept as is and serves as a witness.

In the other beakers, the following products are dissolved
Beaker n 2
Calcium Chloride, CaCl2 5g (10 g / l slurry)
Beaker n 3
Ferric chloride, FeCl3,6H20 2.5g (5g / liter of slurry)
Beaker n 4
Calcium sulphate, CaSO4,2H20 5g (10g / liter of slurry)
Beaker n 5
Iron sulphate, FeSO4,7H20 2.5g (5g / liter of slurry)
Beaker No. 6
Calcium chloride, CaCl2 5g (10g / liter of slurry) plus Ferric chloride FeCl3,6H20 2.5g (5g / liter of slurry)
Beaker No. 7
Calcium sulphate, CaSO4,2H2O 2.5g (10g / liter of slurry) plus Iron sulphate, FeSO4,7H2O 2.5g (5g / liter of slurry)
Beaker n 8
Yucca shidigera extract (Deodorase, Alltech ND) (2g / liter of slurry)
Twenty minutes after the introduction of each slurry treatment, a six-person panel is asked to sniff each beaker to determine the odor of the manure it contains.

 The results reported in Table I clearly show that the calcium salts, in the presence of iron salts, have eliminated the bad smells of pig manure.

Table I: Results of Example 1

<tb> Beaker <SEP> n <SEP> Treatment <SEP> Odor
<tb><SEP> 1 <SEP> Control <SEP> Complex, <SEP> nauseating, <SEP> spicy,
<tb><SEP> tenacious, <SEP> characteristic <SEP> of <SEP> slurry <SEP> of
<tb><SEP> pigs
<tb><SEP> 2 <SEP> CaCl2 <SEP> Odor <SEP> nauseating, <SEP> sulfur
<tb><SEP> 10g / l
<tb><SEP> 3 <SEP> FeCl3,6H2O <SEP> Severe <SEP> odor <SEP> of urine <SEP> aged
<tb><SEP> 5g / l
<tb><SEP> 4 <SEP> CaSO4,2H20 <SEP> Odor <SEP> nauseating, <SEP> sulfur
<tb><SEP> 10g / l
<tb><SEP> 5 <SEP> FeSO4,7H20 <SEP> Severe <SEP> odor <SEP> urine <SEP> aged
<tb><SEP> 5g / l
<tb><SEP> CaCl2,10g / l <SEP> Odor <SEP> of <SEP> undergrowth
<tb><SEP> 6 <SEP> + <SEP> (humus)
<tb><SEP> FeCI3,6H20,5g / l <SEP>
<tb><SEP> CaSO4,71-120,10g / l <SEP> Odor <SEP> of <SEP> undergrowth
<tb><SEP> 7 <SEP> + <SEP> (humus)
<tb><SEP> FeSO4,7H2O, 5g / l <SEP>
<tb><SEP> 8 <SEP><SEP> extract <SEP> Same <SEP> smell <SEP> as <SEP><SEP> slurry <SEP> control
<tb><SEP> Yucca <SEP> schidigera
<tb><SEP> 2g / l
<Tb>
EXAMPLE 2
500 ml of pig manure are introduced into each of the 7 beakers of 2 liters capacity.

Apart from the control beaker, the following products are dissolved in the other beakers
Beaker n 2
Calcium sulphate, CaSO4,2H20 5g (10g / l slurry)
Beaker n 3
Copper sulphate, CuS04.5H2O 2.5g (5g / l slurry)
Beaker n 4
Zinc sulphate, ZnSO4,7H20 1.5g (3g / l slurry)
Beaker n 5
CaSO4.2H20, 5g + CuSO4.5H2O, 2.5g
Beaker n 6 CaSO4,2H20, 5g + ZnSO4,7H20, 1,5g
Beaker n 7
CaSO4.2H2O, 5g + CuSO4.5H2O, 1g (2g / l of slurry) + ZnSO4.7H2O, 0.5g (1g / l of slurry)
Twenty minutes later, the jury sniffs the beakers as before.

 The results in Table II show that calcium sulphate, in the presence of copper or zinc salts, or their combination, is capable of suppressing odors of pig manure.

Table II: Results of Example 2

<tb> Beaker <SEP> n <SEP> Treatment <SEP> Odor
<tb><SEP> 1 <SEP> Control <SEP> Complex, <SEP> nauseating, <SEP> spicy,
<tb><SEP> tenacious, <SEP> characteristic <SEP> of <SEP> slurry <SEP> of
<tb><SEP> pigs
<tb><SEP> 2 <SEP> CaSO4,2H20 <SEP> Odor <SEP> nauseating, <SEP> sulfur
<tb><SEP> 10g / l
<tb><SEP> 3 <SEP> CUSO4,5H2O <SEP> Severe <SEP> odor <SEP> urine <SEP> aged
<tb><SEP> 5g / l
<tb><SEP> 4 <SEP> ZnSO4,7H20 <SEP> Severe <SEP> odor <SEP> urine <SEP> aged
<tb><SEP> 3g / l
<tb><SEP> 5 <SEP> CaSO4,2H2O, <SEP> 10g / l <SEP> Odor <SEP> of <SEP> undergrowth
<tb><SEP> + <SEP> (humus)
<tb><SEP> CuSO4,5l-I2O, <SEP> 5g / l
<tb><SEP> 6 <SEP> CaSO4,21120, <SEP> 10g / l <SEP> Odor <SEP> of <SEP> undergrowth
<tb><SEP> + <SEP> (humus) <SEP>
<tb><SEP> ZnSO4,7H2O, <SEP> 3g / l
<tb><SEP> CaSO4,2H20, <SEP> 10g / l <SEP> Odor <SEP> of <SEP> undergrowth
<tb><SEP> + <SEP> (humus)
<tb><SEP> 7 <SEP> CuSO4.5H2O, <SEP> 2g / l
<tb><SEP> ZnSO4,7H20, <SEP> lg / l <SEP>
<Tb>
EXENIPLE 3
500 ml of pig manure are introduced into each of the 5 beakers, as before.

 The manure treatments were as follows.

Beaker n 1
Witness
Beaker n 2
Magnesium Chloride, NIgCl 2, 6H 2 O, 5g (10g / l slurry)
Beaker n 3
Magnesium sulphate, MgSO 4, 7H 2 O, 5 g (10 g / l slurry)
Beaker n "4 MgCl 2, 6H 2 O, 5 g + FeSO 4, 7H 2 O, 1.5 g (3 g / l of slurry)
Beaker n MgSO 4, 7H 2 O, 5 g + FeSO 4 · 7H 2 O, 1.5 g (3 g / l of slurry).

 Twenty minutes later, the jury sniffs the beakers as before.

 The results in Table III show that magnesium chloride and sulfate, in the presence of iron sulfate, are also effective in deodorizing pig manure.

Table III: Results of Example 3

<tb> Beaker <SEP> n <SEP> Treatment <SEP> Odor
<tb><SEP> 1 <SEP> Control <SEP> Complex, <SEP> nauseating, <SEP> spicy,
<tb><SEP> tenacious, <SEP> characteristic <SEP> of <SEP> slurry <SEP> of
<tb><SEP> pigs
<tb><SEP> 2 <SEP> MgCl2,6H20 <SEP> Odor <SEP> nauseating, <SEP> sulfurous
<tb><SEP> 10g / l
<tb><SEP> MgSO4,7H20 <SEP> Odor <SEP> nauseating, <SEP> sulfur
<tb><SEP> 10g / l
<tb><SEP> MgCl2,6H20, <SEP> 10g / l <SEP> Odor <SEP> of <SEP> undergrowth
<tb><SEP> 4 <SEP> + <SEP> (humus)
<tb><SEP> FeSO4,7H20, <SEP> 3g / l <SEP>
<tb><SEP> MgSO4,7H20, <SEP> 10g / l <SEP> Odor <SEP> of <SEP> undergrowth
<tb><SEP> 5 <SEP> + <SEP> (humus)
<tb><SEP> FeSO4,7H20, <SEP> 3g / l
<tb> EXENIPLE 4
In each of the 2 beakers of 2 liters of volume, 500 ml of slurry of laying hens are introduced, and the following treatments are carried out:
Beaker n 1
Witness
Beaker n 2
CaCl 2, 2.5 g (5 g / l of slurry) + FeSO 4, 7H 2 O, 2.5 g (5 g / l of slurry)
Twenty minutes later, the jury sniffs the beakers as before.

 The results in Table IV show that the treatment is also effective against chicken manure.

Table IV: Results of Example 4

<tb> Beaker <SEP> n <SEP> Treatment <SEP> Odor
<tb><SEP> 1 <SEP> Control <SEP> Nausea
<tb><SEP> 2 <SEP> Cal2, <SEP> 5g / l
<tb><SEP> + <SEP> Odor <SEP> sweetish
<tb><SEP> FeSO4,7H20, <SEP> 5g / l
<Tb>
EXAMPLE 5
As in Example 4, the slurry of hens is replaced by 500 ml of cattle manure.

The treatments are
Beaker n 1
Witness
Beaker n 2 CaCl 2, 2.5 g (5 g / l of manure) + FeSO 4 · 7 I 1/2, 1 g (2 g / l of slurry)
Twenty minutes later, the jury sniffs the beakers as before.

 Table V shows that the treatment is also effective against cattle manure.

Table V: Results of Example 5

<tb> Beaker <SEP> n <SEP> Treatment <SEP> Odor
<tb><SEP> 1 <SEP> Control <SEP> Odor <SEP> nauseating
<tb><SEP> 2 <SEP> CaCl2, <SEP> 5g / l <SEP> Odor <SEP> acidulous <SEP> reminding
<tb><SEP> + <SEP> l <SEP>'silage
<tb><SEP> FeSO47H20 <SEP> 2g / l
<Tb>
EXAMPLE 6
The objective of the test is to assess the odor of pig manure treated with CaSO4,2H20 + FeSO4,7H20 at field application.

 In a ton of slurry of 3 cubic meters, having a pressure spraying system, 15 kg of CaSO 4 .2H 2 O + 6 kg of FeSO 4 · 7H 2 O are introduced.

 The ton is then pumped with pig manure. The turbulence created by the filling allows the calcium and iron salts to dissolve. As soon as the filling, which lasts for 20 minutes, is completed, spreading is carried out by spraying the manure thus treated, on a strip of 120 m × 7 m in a meadow, the ton being towed by a tractor.

 The same operation is repeated, with untreated manure serving as a control, on another parcel of meadow equivalent.

The odor of manure, treated and control, is assessed during and immediately after spreading, downwind, 50 meters from the spreading site, by a panel of 8 people who refer to a scale of normalized intensity. The odor products of the reference scale consist of aqueous solutions of pyridine whose concentrations (volume / volume of water) and odor intensity are

<tb><SEP> Concentration <SEP> Odor Intensity <SEP>
<tb> (volume / volume)
<tb><SEP> 102 <SEP> Very <SEP> strong
<tb><SEP> 103 <SEP> Strong
<tb><SEP> 104 <SEP> Average <SEP>
<tb><SEP> 105 <SEP> Low
<tb><SEP> Very <SEP> weak
<Tb>
The assessment of the odors by the jury is as follows
Treated manure
Low intensity
Sweetish odor
Sample slurry
Strong intensity
Complex odor, nauseating, pungent, persistent, characteristic of pig manure.

Claims (9)

 1. A method of rapid deodorization of manure, characterized in that dissolved in slurry at least one soluble salt of alkaline earth metal and at least one soluble salt of a metal of the columns VIII, IB and IIB.  2. Method according to claim 1, characterized in that the soluble salts of alkaline earth metals are chloride and / or calcium sulfate.  3. Method according to claim 1, characterized in that the soluble salts of alkaline earth metals are chloride and / or magnesium sulfate.  4. Method according to one of claims 1 to 3, characterized in that the soluble salts of metals are chlorides and / or iron sulfates.  5. Method according to one of claims 1 to 3, characterized in that the soluble salts of metals are chloride and / or copper sulfate.  6. Method according to one of claims 1 to 3, characterized in that the soluble salts of metals are chloride and / or zinc sulfate.  7. Method according to one of claims 1 to 6, characterized in that the soluble salts of alkaline earth metals are a mixture of calcium and magnesium salts.  8. Method according to one of claims 1 to 7, characterized in that the soluble metal salts are a mixture of iron salts, copper and zinc.  9. Method according to one of claims 1 to 8, characterized in that the contribution of each soluble salt is 0.5 to 10 grams per liter of slurry.