LU85416A1 - SOLID ORGANO-MINERAL FERTILIZER COMPOSITION AND PROCESS FOR PREPARING THE SAME - Google Patents

Description

! ! * \ "Solid composition of organo-mineral complex fertilizer and process for its preparation."

The present invention relates to a solid composition 1 5 of organo-mineral complex fertilizer soluble in water.

| The invention also relates to a process for preparing this fertilizer composition.

I French patent N ° 7923256 describes and claims a process for the desalination of effluent from pro- | .

S10 yielded industrial sugar fermentation by processing these. effluents either with a mineral acid or with an [organic acid in the presence of a relatively volatile solvent.

This process mainly used to precipitate së ~; the potassium salts of beet molasses vinasses, which, after having been freed from most of their potassium content, form a compound! setting valid for fodder which is especially intended for ruminants as described in French patent application K 82 82259-! 20 The present invention is essentially based on the observation that the products from desalination: by l tallow acid, in the presence of an organic solvent, effluents from a fermentation process of sugars, in addition to being highly concentrated in potassium, are free from organic substances and also contain relatively large amounts of other mineral elements as well as useful organic products j | lj which pass into the unmodified state; or practically unmodified ^ L Âv ··· - ^ »» · * φ 2 * · through fermentation and desalination processes.

Consequently, according to the present invention, said solid products originating from the desalination stage are used after an appropriate preliminary integration; as components for fertilizer compositions.

Consequently, the present invention relates to a solid composition of organo-mineral complex fertilizer comprising: a) the solid product originating from desalination with sulfuric acid - and in the presence of a organic solvent, of an effluent from industrial processes for the fermentation of sugars (vinasses); b) at least either an organic compound or a mineral compound carrying phosphorus and / or nitrogen.

The fertilizer composition according to the present invention suitably contains at least 3% of its weight of total nitrogen (with at least 1.5% by weight in the form of organic nitrogen), at least 4% by weight of phosphorus (expressed in P ^ O ^) * at m ° Lns 5% by weight of potassium (expressed in K ^ O), and at least 8% by weight of organic carbon.

The raw materials suitable for the preparation of the component indicated in a) above of the fertilizer composition according to the present invention are the effluents pro; coming from industrial processes for the fermentation of sugars, such as for example the effluents from the industrial fermentation of molasses or more generally from the fermentation of solutions containing mistletoe are obtained by extraction from plants such as beet | sugar, sugar cane, and sorghum. These effluents are I 9 generally designated by “vinasses”. As raw materials, other effluents from industrial sugar fermentation processes can be used, such as, for example, residues from the manufacture of citric acid, glycerin, glutamic acid. , lactic acid, butyl alcohol and acetone and antibiotic substances. All these possibilities describe 7 \ * Λ; 3 tes previously are based on the observation that the fermentation processes, which are carried out on extracts * of plants containing sugar (are active on the carbohydrates contained in the raw material while practically not-5 the minerals and proteins initially contained in the material subjected to fermentation. Subsequently, all these raw materials will be designated by the term "Vinasse".

According to the process which is the subject of the present invention, a vinasse containing from 35 to 65% by weight and preferably from 50 to 60% by weight of dissolved solid products is brought into contact with sulfuric acid. For celadon preferably uses concentrated sulfuric acid, for example sulfuric acid having a specific mass of about 1.84 kg / 1.

However, sulfuric acid diluted with water can be used, although it is not generally advantageous to use sulfuric acid having a specific gravity less than 1.69 kg / 1 The quantity of sulfuric acid to be added to the vinasse depends on the potassium content of the

L

p 20 vinasse itself. Generally an amount of sulfuric acid is used between 1.3 and 1.8 kg / kg of potae-; sium in vinasse. The contacting between the vinasse and sulfuric acid is suitably carried out in a closed laboratory container equipped with stirring means. A fundamental characteristic of the process according to the present invention is that the desalination reaction is of the vina.sse is carried out in the presence of an organic solvent which is soluble in the reaction medium and is inert with respect to the other constituents of the reaction mixture.

‘30 Organic solvents which are suitable for this purpose,! v are lower aliphatic alcohols (such as methanol, and ethanol), and ketones (such as acetone and methylethyl and one).

Among these solvents, ethanol is especially preferred because of its low toxicity, or it is easy to obtain at 4 × 4 ht L, inexpensive and, because this solvent makes it possible to obtain said precipitate having physical characteristics such as subsequent treatment of separation, drying and mixing ~ ge are made easy. The organic solvent used need not be anhydrous, and moreover, the amount used of this solvent is not critical, although it is preferable to use it in an amount of 10 to 25 parts by volume for 100 volumes of vinasse.

In the practical embodiment of the process according to the present invention, sulfuric acid is added to the vinasse which is stirred in a closed laboratory container.

After a few minutes (for example after 3 minutes), the organic solvent is added to the charge with stirring. After an additional period of approximately 20 to 60 minutes, the stirring is stopped, the solid product which has precipitated is then separated, for example by centrifugation.

; All the operations described above are carried out at room temperature (20-25 ° C) or at temperatures close to room temperature.

The precipitated and separated solid material is then subjected to a drying stage which is suitably carried out at temperatures below 130 ° C and, if necessary, at a pressure below atmospheric pressure.

Component a) of the fertilizer composition according to the present invention is thus obtained. This constituent a) contains primary chemical elements responsible for the fertilizing power and more particularly potassium and nitrogen, secondary elements such as calcium, magnesium and sulfur, and trace elements such as manganese, zinc, copper, boron and iron. This component a) also contains organic products which cause this component a) to contain a high percentage of organic carbon of biological origin, and amino acids carrying organic nitrogen are also present.

More particularly, when materials t are used; 5

U

\ - first consisting of effluent from vinasse from the distillation processes of sugar beet molasses or sugar cane molasses or by effluents of vinas from citric acid production from beet molasses, can obtain component a) of the fertilizer composition with a potassium content generally greater than 10% and concretely ^ of 15% by weight, with an organic carbon content greater than 10%. and ^ concretely ^ between 15% and 25% by weight, and 10 with a non-ammoniacal nitrogen content of the order of 0.5% to 5% by weight.

The solid fertilizer composition according to the present invention is prepared by mixing component a) described above with component b) comprising at least one organic and / or inorganic compound carrying phosphorus and / or nitrogen. . As component h), any of the organic or mineral fertilizers currently known in the art, such as, for example, urea, nitrates and ammonium salts, can be used as nitrogen carriers; blood meal and concentrated vinasses from beet molasses, as nitrogen and organic carbon carriers; superphosphates such as, for example, the supertriple, phosphoric acid or its salts, as carriers of phosphorus.

Of course, if desired, a potassium bearing salt, such as potassium chloride and potassium sulfate, can also be added to the composition.

"The ratio of the amounts of component a) and component b) of the composition is adjusted according to the nature of these constituents as well as according to the desired titers of nitrogen, phosphorus and potassium in the composition itself.

An advantage of the present invention is, in fact, that it is possible to obtain a solid composition of mineral organ complex fertilizer with a desired and constant titer of nitrogen, phosphorus and potassium, even when using as raw material the effluents coming from industrial sugar fermentation processes, the characteristics of which are variable.

In some cases, the solid composition of organo-mineral complex fertilizer according to the present invention is soluble in water and has the characteristics of a good fertilizer, not only chemically, but also the fact that it comes from a vegetable-only raw material which has first been subjected to processes of essentially biological character, and therefore is completely free of phytotoxic substances.

An advantage resulting from the use of the fertilizer composition according to the present invention is that part of the fertilizers which have been extracted from the soil during the vegetative cycle of the sugar plants, can be recovered and used again as fertilizer; and that, in addition, the pollution problems posed by the effluents of industrial fermentation processes can be resolved simultaneously. The present invention is illustrated by the following descriptive and nonlimiting examples.

EXAMPLE 1

13 kg of concentrated sulfuric acid are added to a closed laboratory container equipped with stirring means containing 250 kg of vinasse from the distillation of concentrated beet molasses, which contains 52% by weight of dissolved solid matter, (density 1.84 kg / 1) and after a few minutes with stirring, 33 kg of a hydro-ethaηο1ique solution (density 0.82 kg / 1) are added.

After having stirred slowly for about 1 hour, the resulting precipitate is separated by centrifugation using a decanter centrifuge, sent to a drying oven operating at 80 ° C, under vacuum, and weighed. 41 kg of a product are thus obtained which will be designated subsequently by "saline 35". Potassium ", which is subjected to chemical analysis. The results £ 7 y of the analysis are shown in Tables 1 and 2.

More particularly, the main chemical characteristics of potassium saline are indicated in Table 1 * expressed as a percentage by weight relative to the dry matter and the amino acids which are contained in potassium saline are indicated in Table 2. , the concentrations being always expressed as a percentage by weight relative to the * dried product.

ί. TABLE 1 i - | 10 Ashes 58.22 • Organic matter 41.78 \ | Total nitrogen 2.84 | Ammoniac nitrogen 0.16 \ Organic carbon 17.50 15 Hydrogen 2.45 |

Potassium 14.99 i '| S od ium 4.80 'Calcium 2.03

Magnesium 1.20 20 Manganese 0.23

Iron 0.091

Boron 0.0070 i Cu drunk 0.0023

Zinc 0.0095 i> i 25 Sulfates 23.08 S Phosphates 0.25

Chlorides 1.85; TABLE 2

Lysine 0.05 30 Histidine 0.03 I

Arginine 0.03 'Aspartic acid 0.36 il Threonine 0.17 Serene 0.16 35 Glutamic acid 3.95 / 8 TABLE 2 (continued) l Phenylalanine 0.06

Glycine 0.21

Alanine 0.45 5 Proline 0.17 Methionine 0.03

Isoleucine 0.18

Leuc ine 0.15

Tyros ine 0.16 10 Betaine 4.12

The potassium salt therefore has a titer of N: P ^ 0 ^: K ^ OïMgO respectively of 3: 0: 18: 2.

The potassium salt which has been prepared as indicated above is used as a constituent in the formulation of organo-mineral fertilizers with different titers of N, PO and KO.

25 2

More particularly, in a kneader-grinder-mixer mill, urea ^ (NH ^) ^ HPO ^ and / or supertriple is added to potassium saline in the amounts indicated in Table 3. The mixtures thus obtained, homogenized and oranules les are examples of fertilizer compositions according to the present invention.

TABLE 3

Organo-fflihéral fertilizer for basic fertilization '4-15-12 ·

25 Constituents N P 0_ KO

2 5 2 (N: P ^ O ^: K ^ 0) (%) (%) (%) potassium saline 67.8 1.9 Γ0.1 12.2 (2.82: 0.18: 18) 30 Supertriple 27.7 --- 12.2 ---- (0: 44: 0)

Urea 4.5 2.1 ------ ----- (46: 0: 0)> 100.0 4.0 12.3 12.2 9 U # - ψ b) Organo-mineral fertilizer for basic fertilization I 7-13-13 g Constituents NP 0 ^. K 0 | (N: P205: K20) (%) (%) '(%) (%) | Potassium saline 72.2 2.0 0.1 13.0 1 (2.82: 0.18; 18) 11! (NH4) 2HPOa 27.8 5.0 12.8 ---- 1 (19: 46: 0)% 9 I. 100 7.0 12.9 13.0 | c) Organo-mineral fertilizer for corn fertilization I indoors 17-8-10 I Constituents N ^ 2 ^ I 15 (K: P205: K20) U) <%) (%) (%) f | Potassium saline 55.6 1.6 0.1 10.0 I (2.82: 0.18: 18) I * (KH.) HF0 17.4 3.1 8.0 - --- 1 4 2 4 | 20 08 = 46 = 0) | Urea 27.0 12.4 --- ------ 1 (46: 0: 0) 100.0 17.1 8.1 10.0; | In the compositions a), b) and c) described above, the amount of organic carbon which results therefrom is respectively 11.8; 12.6; and 9.7.

1! EXAMPLE 2 i 'In a closed laboratory container equipped with means; stirrer containing 250 kg of vinasse from the distillation of beet molasses, concentrated to a content of: | 59% of dissolved solid, 15 kg of concentrated sulfuric acid 1 (density 1.84 kg / l) are added, and after a few minutes of stirring, 33 kg of an ethanolic hydro · f solution ( density 0.82 kg / l).

35 * After having stirred slowly for about an hour, i i I / 1 1 * · * φ »Λ ίο.

+ · Ί *.

! & the precipitate thus obtained is separated by centrifugation using a decanter centrifuge. The wet product} * (65.2 kg at 65% dry matter) is introduced into a second laboratory container and mixed with 32 kg of a hydro-ethanolic solution (density 0.82 kg / 1). i After shaking quickly for a few minutes, | the precipitate is separated by centrifugation and it is sent to a bare, dry mixer 1 having been operating below atmospheric pressure and equipped with a device for recovering the condensate.

; 32.6 kg of granulated product are thus obtained, the chemical composition of which is indicated in table A, in the | which the concentration values are expressed as a percentage by weight relative to the dry matter.

; 1 5 TABLE A

Ashes 7 A, 5 | Organic matter 25.5 days! “Total nitrogen 2.0 r d! Trace ammonia nitrogen I; | j 20 Organic carbon 12.0 i.

I · j: Hydrogen 2.1 I Potassium 19.3 dd Magnesium 1.1 d Phosphates 0.38 25 The potassium saline thus obtained therefore has the title of N: P205: K ^ O: MgO of 2: 0: 23 : 1.

! This potassium saline is mixed with synthetic products and in addition with products carrying nitrogen and organic carbon, more particularly with concentrated concentrates from beet molasses and; _ blood meal, in the quantities indicated in table 5.

Homogenized and granulated diapers are examples of fertilizer compositions according to the present invention.

f 11 *; TABLE 5

a) Organo-mineral fertilizer for basic fertilization 4-12-14 Constituents N PO KO

i 2 5 2 | ^ (N: P205: K20) (%) (%) (%) (7.) i * _____________ _______________ [I Potassium salt 62.5 1> 25 14.50 1 5 (2.0: 0: 23.2 ) i I; . Supertriple 27.5 ---- 12.10 ----- | (0: 44: 0) | '' Blood flour 5.0 0.50 0.04 0.03 (10.0: 0.9: 0.6) 10 Urea 5.0 2.30 ---- i (46.0: 0: 0 ) i ___ _______ _ i 100.0 4.05 12.14 14.53 | b) Organo-mineral fertilizer for fertilizing fields of j ,. forage 7-10-6 S Constituents N PO K n 2 5 2 (N: P 0: K 0) (Z (Z) (Z) (Z) 2 5 2 - - - - - —— - --—-- -— - - - - - - - - - - - - T - - - - jl Potash salt 7 2.0 1.44 ---- 1 6.70 J (2.0: 0: 23.2) 20 (NH) HPO 21.8 3.92 1 0, 03 ------ | (18.0: 46.0: 0)! Concentrated vinasses 3.5 0.16 0.06 I (4.67: 0: 1.75) I Urea 3.7 1.70 ---- ---- | 2 5 (46.0: 0: 0) ______ ______ _____ ____ j  100 7.22 10.03 16.76 Λ jl 4 * »·» «- - 12 * c) Organo-mineral fertilizer for fertilization of market gardens 5-9-18.

Constituents N PO KO

2 5 2 (N: P2O5: K20) (Z) (Z) (Z) (%)

Potassium salt 7 9, 0 1.58 --------- 18.30 (2.0: 0: 23.2) (NV2pV 1 9.5 3.51 8.97 ------ (18.0: 46, 0: 0) 10 Concentrated vinasses 1, 5 0.07 ----- 0.03 (4.67: 0: 1.75) 100 5.16 8.97 18.33 EXAMPLE 3

In a closed laboratory container equipped with stirring means, containing 247 kg of vinasses from the distillation of cane sugar molasses, concentrated at 38% of dissolved solid, 13.5 kg of concentrated sulfuric acid ( density 1.84 kg / l) and, after a few minutes of stirring, 34 kg of a hydro-ethanoli-20 solution are added (density 0.82 kg / l). After having stirred slowly for about an hour, the precipitate thus obtained is separated by centrifugation using a decanter centrifuge, sent to a drying oven operating at 80 ° 0 under vacuum, and weighed.

25 33.2 kg of product are thus obtained which is subjected to chemical analysis, the results of which are shown in Table 6, the concentration values being expressed as a percentage by weight relative to the dry product.

TABLE 6 3 0 Ash 61.40

Organic materials 38.60

Total nitrogen 0.52

Trace ammonia nitrogen

Organic carbon 13.14 35 sJ Hydrogen 1.78 * Λ - * »* 13

ί_ TABLE 6 J ^ u_itejL

Potassium 15.47

Magnesium 0.7 0

Phosphates 0.63, 5 The title of the potassium saline thus obtained is consequently: N: P ^ 0 0: MgO = 0.5: 0.5: 18.5: 1-

By incorporating this potassium saline, organ-mineral fertilizer formulations are obtained which are similar to those indicated in Examples 1 and 2 above.

1 0 EXAMPLE 4

In a closed laboratory container equipped with stirring means, containing 253 kg of vinasse effluents from: the production of citric acid from beet molasses, these vinasses having been concentrated to a content of 57 _% of dissolved solid matter, 14.5 kg of concentrated sulfuric acid (density 1.84 kg / l) are added, and after a few minutes of stirring, 34 kg of a hydro-ethanolic solution (density 0.82 kg / l). After having stirred for about 1 hour, the precipitate thus obtained is separated by centrifugation using a basket centrifuge, sent to a drying oven operating at 80 ° C under vacuum and weighed. 69.6 kg of product are thus obtained which is subjected to chemical analysis, the results of which are indicated in percentage by weight relative to the dry product in product 7.

25 TABLE 7

Ashes 39.20

Organic matter 61.80

Total nitrogen 4.55

Ammonia nitrogen 0.31 30 Organic carbon 24.90

Hydrogen 3.36

Potassium 11.79

Magnesium 0.43 I Phosphates 0.46 ('' '!,

The potassium saline thus obtained therefore has a titer ^ OrMgO of 4.5: 0.3: 14: 1.

By incorporating this potassium saline, organo-mineral fertilizer formulations similar to those obtained in Examples 1 and 2 above are obtained.

: /

Claims (4)

2. Composition according to Claim 1, characterized in that the constituent a) is obtained by bringing the vinasse into contact with sulfuric acid then by adding to the mixture thus obtained an organic solvent ^ chosen from the class of alcohols lower and lower cétones, and separating and finally drying the precipitate thus obtained. 3. Composition according to claim 1, characterized in that, in the preparation of component a), a vinasse is used having a solid content between 35% and 65% by weight and that sulfuric acid is used with a density between 1.69 and 1.84 kg / 1, in an amount between 1.3 and 1.8 kg per kg of potas sium in vinasse. 4. Composition according to claim 1, characterized in that in the preparation of component a), an amount of said organic solvent is used between 10 and 25 parts by volume per 100 parts by volume of vinasse. 5. Composition according to claim 1, characterized in that the said organic solvent is ethanol. 7P 1 .. * -. ! <16 • »tf 6. Composition according to claim 1, characterized in that component b) is chosen from the class of urea, nitrates, ammonium salts," (superphosphates, phosphoric acid, salts of phosphoric acid, blood meal and concentrated vines. X!!} j - ii 4 ji H} iii |! - i 4 g \