CA1230237A

CA1230237A - Solid composition of complex organo-mineral fertilizer and process for preparing it

Info

Publication number: CA1230237A
Application number: CA000456614A
Authority: CA
Inventors: Andrea Robertiello; Leonello Angelini
Original assignee: Eni SpA
Current assignee: Eni SpA
Priority date: 1983-06-15
Filing date: 1984-06-14
Publication date: 1987-12-15
Also published as: DE3422177A1; CH660001A5; NL8401915A; BR8402954A; IT1161939B; DE3422177C2; GB2141419A; FR2557095A1; GB8414851D0; GB2141419B; LU85416A1; IT8321632A0; JPS6081080A; BE899924A; FR2557095B1

Abstract

"SOLID COMPOSITION OF COMPLEX ORGANO-MINERAL FERTILIZER AND
PROCESS FOR PREPARING IT"

ABSTRACT OF THE DISCLOSURE:

Solid composition of complex organo-mineral fertilizer, comprising: a) the solid product from the desalting by means of sulfuric acid and in the presence of an organic solvent, of an effluent from the industrial processes of fermentation of the sugars (vinasse); b) at least one organic or inorganic compound, bearer of phosphorous and/or nitrogen.

Description

~3023~7 The present invention relates to a solid composition of complex organo-mineral, water-soluble fertilizer. The invention relates also to a process for preparing such composition of fertilizer.
The Canadian Patent No. 1.123.653 granted on May 18, 1982, describes and claims a process for desalting the effluents from the industrial fermentation processes of the sugars, by means of the treatment of such effluents with either a mineral or an organic acid, in the presence of a relatively volatile solvent.
This process is mainly used for selectively precipitating the potassium salts from the beet molasses vinasses, which, after having been deprived of the most of their potassium content, form a valuable component for folders, which are mainly intended for polygastric cattle, as it is described in the Canadian Patent Application No.
395.443 filed on February 3, 1982.
The present invention is essentially based on the observation that the products from the desalting by means of sulfuric acid, in the presence of an organic solvent, of the effluent streams from the fermentation process of the sugars, in addition to containing large concentrations of potassium, are free from phytotoxic substances and moreover contain relatively large quantities of other mineral elements, as well as of useful organic products, which pass, unchanged or practically unchanged, through the fermentation and desalting processes. Therefore, according to the present invention, the said solid products from the desalt-in stage are used, after a suitable preliminary integration, as come I

~3C;~23~

pennants for compositions of fertilizers.

The invention therefore provides a water-soluble solid composition of complex organo-mineral fertilizer, comprising:-(a) a product obtained from the desalting of vines from industrial sugar fermentation, the vines having a solid content within the range from 35~ to 65% by weight, the desalting being carried out using (i) sulfuric acid having a specific gravity in the range from 1.69 to 1.84 Kg/l in a quantity within the range from 1.3 to 1.8 kg per kilogram of potassium in the vines, (ii) from 10 to 25 parts by volume, per 100 parts by volume of vines, of an organic solvent inert towards the other components, selected from the group consisting of lower alcohols and lower kittens; and (b) at least one organic or inorganic compound, bearer of phosphorous and/or nitrogen;

said composition containing total nitrogen in a quantity of not less than 3% of its weight (with at least 1.5% by weight of organic nitrogen), phosphorous (expressed as POW) in a quantity of not less than 4% by weight, potassium (expressed as KIWI) in a quantity of not less than 5% by weight, and organic carbon in a quantity of not less than 8% by weight.

Suitable raw materials for preparing the above shown component (a) of the fertilizer composition according to the present invention, are effluents from industrial ~3~)23'7 - pa -fermentation processes of sugars, for instance the effluents from the industrial fermentation of molasses, or more generally, of sugar containing solutions which are obtained by extraction from plants such as the sugar beet, the sugar cane and the sugar sorghum. Such effluents are generally named "vinasses". As raw materials, still other effluents from the industrial fermentation processes of the sugars can be used, such as e.g. the residues from the production of citric acid, glycerine, glut I

__ lactic acid, bottle alcohol and acetone and of the anti-bionic substances. These all previously described posse-abilities are based on the observation that the fermentation processes, which are carried out on sugar containing extracts from plants, are active on the carbohydrates con-twined in the raw material, at the same time leaving the minerals and the proteins initially contained in the material under fermentation, practically unchanged. Here-under, all these raw materials shall be generally indicated as "vines".
According to the process within the purpose of this invention, a vines containing from 35~ to 65~ by weight, and preferably from 50% to 60% by weight of disk solved solids, is placed in contact with sulfuric acid. To this purpose, concentrated sulfuric acid is preferably used, ego sulfuric acid with a specific gravity of about 1.84 kg/l. It is however possible to use aqueous diluted sulfuric acid, even if it is not generally profitable to use sulfuric acid with a specific gravity lower than 1.69 kg/l. The quantity of sulfuric acid to be added to the vines is a function of the potassium title of the vines itself. A quantity of sulfuric acid is generally used, within the range from 1.3 to 1.8 kg/kg of potassium in the vines. The contact between the vines and the sulfuric acid is suitably carried out in a closed reaction vessel, having stirring means.
One fundamental feature of the process according to the present invention, is that the desalting reaction of the vines is carried out in the presence of an organic solvent, which is soluble in the reaction medium, and is inert towards the other components of the reaction mixture.
Organic solvents which are suitable to this purpose, are the lower aliphatic alcohols (such as methanol and ethanol) and the kittens (such as acetone and methyl-- 4 - ~3~37 ethyl-ketone).
The most preferred solvent among these is the ethanol, in view of its low toxicity, large availability at low cost, and as this solvent causes the said precipitate to be obtained with such physical characteristics, as to make the subsequent treatments of separation, drying and blending easy. It is not necessary that the organic solvent used be an hydrous, and moreover the used quantity of such solvent is not critical, although it can be advisably used in the ratio in the range from 10 to 25 parts by volume, per 100 volumes of the vines.
In the practical embodiment of the process according to the present invention, the sulfuric acid is added to the vines, which is being stirred in a closed reaction vessel. A few minutes later (e.g. after 3 minutes), the organic solvent is added to the charge under stirring. After a further time of from 20 to 60 minutes has elapsed, the stirring is discontinued, the precipitated solid is then separated, such as by centrifuging. All the previously described operations are carried out at room temperature (20 - 25C), or at temperatures close to the room temperature.
The precipitated and separated solid matter is then submitted to a drying stage, which is suitably effected at temperatures lower than 130C, and possibly under a lower than atmospheric pressure.
The component a) of the fertilizer composition according to the present invention is thus obtained. Such a) component contains primary chemical elements of the fertilizer power and more particularly, potassium and nitrogen, secondary elements such as calcium, magnesium, and Selfware, and trace elements, such as manganese, zinc, copper, boron and iron. The said a) component contains also organic products, which cause the said a) component to ~3~2~37 contain a high percentage of organic carbon from biological origin, and amino acids too are present, which are bearers of organic nitrogen.
More particularly, when raw materials are used, which consists of vines effluents from the distillation processes of the beet molasses, or of the sugar cane molasses, or vines effluents from the production of citric acid from the beet molasses, it is possible to obtain the a) component of the fertilizer composition with a potassium title generally higher than 10% and typically of 15% by weight, with an organic carbon content higher than 10% and typically comprised within the range from 15% to 25% by weight, and with a content of non ammonia nitrogen of the order from 0,5% to 5% by weight.
The solid composition of fertilizer according to the present invention is prepared by mixing the above described a) component with a b) component comprising at least one organic and/or inorganic compound, bearer of phosphorous and/or nitrogen. As the b) component, any organic or inorganic fertilizer actually known in the art can be used, such as for instance urea, nitrates and ammonium salts as bearers of nitrogen; blood meal and con-cent rated vinasses from beet molasses as bearers of nitrogen and organic carbon; super phosphates, such as for instance super triple, phosphoric acid or its salts, as bearers of phosphorous.
Obviously, if desirable, also a potassium bearing salt can be added to the composition, such as potassium chloride and potassium sulfite.
The ratio of the quantities of the a) and of the b) components of the composition is adjusted as a function of the nature of these components, as well as of the wished titles of nitrogen, phosphorous and potassium in the combo-session itself.

An advantage of the present invention is indeed that it is possible to obtain a solid composition of complex organo-mineral fertilizer with a desired and constant title of nitrogen, phosphorous and potassium, even when using, as the raw material, the effluents from the industrial fermentation processes of the sugars, whose characteristics are variable.
In any cases, the solid composition of complex organo-mineral fertilizer according to the present invention is soluble in water, and has the characteristics of a good fertilizer not only from the chemical viewpoint, but also in that it is derived from a solely vegetable raw material, which has been preliminary submitted to processes of fundamentally biological character, and is therefore completely free of phytotoxic substances.
An advantage resulting from the use of the fertilizer composition according to the present invention, is that a part of the fertilizing elements which have been withdrawn from the soil during the vegetative cycle of the sugar plants, can be recovered and used as fertilizer again, and in addition to this, at the same time eliminating the pollution problems arising from the effluents of the industrial fermentation processes.
The following experimental Examples are illustrative only, and in no way they are to be considered as limitative of the invention.

Example In a closed reaction vessel equipped with stirring means, containing 250 kg of vinasses from the distillation of concentrated beet molasses, containing 52~ by weight of dissolved solid matter, 13 kg of concentrated sulfuric acid (specific gravity 1.84 kg/l) are added, and, after a few I, .
'`'~;

_ 7 _ ~23~3~

minutes under stirring, 33 kg of aqueous ethanol (specific gravity 0.82 kg/l) are added.
After about one hour of slow stirring, the result-in precipitate is separated by centrifuging, by means of a decanter centrifuge, sent to a drying oven operating at 80C, in the vacuum, and weighed. 41 kg of a product are thus obtained, which will be referred to hereunder as "potassic saline", which is submitted to chemical analysis.
The results of the analysis are shown in the Tables 1 and 2.
More particularly, the main chemical characters-tics of the potassic saline are shown in Table 1, as expressed as by weight on a dry matter basis, and in Table

2 the amino acids are shown, which are contained in the potassic saline, the concentrations being always expressed as of the weight of the dried product.

Table Ashes 58.22 Organic matter 41.78 Total nitrogen 2.84 Ammonia nitrogen 0.16 Organic carbon 17.50 Hydrogen 2.45 Z5 Potassium 14.99 Sodium 4.80 Calcium 2.03 Magnesium 1.20 Manganese 0.23 Iron 0.091 Boron 0-0070 Copper 0.0023 Zinc 0.0095 Sulfites 23.08 - 8 - ~302~

Phosphates 0.25 Chlorides 1.85 Table 2 Lawson 0.05 Histidine 0.03 Arginine 0.03 Aspartic acid 0.36 Threonine 0.17 Shrine 0.16 Glutamic acid 3.95 Phenylalanine 0.06 Gleason 0.21 Ala nine 0.45 Praline 0.17 Methionine 0.03 Isoleucine 0.18 Lawson 0.15 Tarzan 0.16 Button. 4.12 The potassic saline has therefore a title N:P2O5: K2O:MgO respectively of 3:0:18:2.
The potassic saline which has been prepared as previously shown, is used as a component in the formulation of organo-mineral fertilizers, with different titles of N, POW and KIWI.
More particularly, in a mixer-granulation mill, urea, (NH4)2HPO4 and/or super triple are added to the potassic saline, in the quantities shown in Table 3. The so obtained mixtures, homogenized and granulated, are examples of fertilizer compositions according to the present invention.

3~1~3~7 Table 3 a) Organo-mineral fertilizer for base manuring 4-12-12 Components 2 5 KIWI

(N:P25:K2)(%) (%)(%) (%~

Potassic saline 67.81.9 0.1 12.2 (2.82:0.18:18) Supertriple27.7 --- 12.2 ----(0:44:0) Urea 4.5 2.1 --- ----(46:0:0) 100.0 4.012.3 12.2 b) Organo-mineral fertilizer for base manuring 7-13-13 Components 25 KIWI

(N:P25:K2)(%) (%)(%) (%~
_ Potassic saline 72.2 2.0 0.1 13.0 (2.82:0.18:18) ( 4)2 4 27.8 5.012.8 --(18:46:0) 100 7.012.9 13.0 c) Organo-mineral fertilizer for indoor maize manuring - lo- ~3~37 Components 2 5 KIWI

(N:P25:K2) (%) (%) (%~ (%~

Potassic saline 55.6 1.6 0.1 10.0 (2.82:0.18:18) ( 4)2 4 17.4 3.1 8.0 ----(18:46:0) Urea 27.0 12.4 ---- ----(46:0:0) 100.0 17.1 8.1 10.0 In the compositions a), b) and c) previously described, the cantata of organic carbon resulted to be 11.8; 12.6; and 9.7 respectively.

Example 2 inn a closed reaction vessel equipped with stirring means, containing 250 kg of vines from the distillation of beet molasses, concentrated to a content of 59% of dissolved solid matter, 15 kg of concentrated sulfuric acid (specific gravity 1.84 kg/l) are added, and, after a few minutes of strung, 33 kg of aqueous ethanol (specific gravity 0.82 kg/l) are added.
After about one hour of slow stirring, the precipitate thus obtained is separated by centrifuging by means of a decanter centrifuge. The moist product (65.2 kg await 65% of dry matter) is introduced in a second reaction vessel and mixed with 32 kg of aqueous ethanol (specific gravity 0.82 kg/l).

023~

After some minutes of rapid stirring, the precipitate is separated by centrifuging, and sent to a drier granulating mill, operating under atmospheric pressure and equipped with a condensate recovery device.
32~6 kg of a granular product are thus obtained, whose chemical composition is shown in Table 4, where the concentration values are expressed as % on the weight of dry matter.

Table 4 Ashes 74.5 Organic matter 25.5 Total nitrogen 2.0 Ammonia nitrogen traces Organic carbon 12.0 Hydrogen 2.1 Potassium 19.3 Magnesium 1.1 Phosphates 0.38 The so obtained potassic saline has therefore a title N:P2O5:K2O:MgO of 2:0:23:1.
Such potasslc saline is integrated with synthetic products, and in addition to these, with nitrogen and organic carbon bearer products, more particularly concern-treated vinasses from beet molasses and blood meal, in the quantities shown in Table 5. The homogenized and granulated or poulticed mixtures are examples of fertilizer compost-liens according to the present invention.

~X~)2;~7 - lo -Table S

a) Organo-mineral fertilizer for base manuring 4-12-14 Components 2 5 KIWI
(N:P205:K20)(~6) (~)(96) I

Potassic saline 62.51.25 -- 14.50 (2.0:0:23.2) Supertriple27.5 --- 12.10 --(0:44:0) Blood flyer 0.500.04 0.03 (10.0:0.9:0.6) Urea 5.0 2.30 -- --(46.0:0:0) 100~0 4.0512.14 14.53 b) Organo-mineral fertilizer for fodder field manuring Components 2 5 KIWI
(N:P2O5:K2O)(~

Potassic saline 72.0 1.44 -- 16.70 (2.0:0:23.2) ( 4)2 4 21.8 3.92 10.03 --(18.0:46.0:0) Cone. vinasses 3.5 0.16 -- 0.06 (4.67:0:1.75) Urea 3.7 1.70 -- --(46.0:0:0) 100 7.22 10.03 16.76 - 13 _ ~Z3~237 c) Organo-mineral fertilizer for market garden manuring Components 2 5 KIWI
(N:P2O5:K2O)(%) (%) (%) (%) Potassic saline 79.0 1.58 --- 18.30 (2.0:0:23.2) (NH4)2PO419.5 3.51 8.97 ___ (18.0:46.0:0) Cone. vinasses 1.5 0.07 --- 0.03 (4.67:0:1.75) 100 5.16 8.97 18.33 Example 3 In a closed reaction vessel equipped with stirring means, containing 247 kg of vinasses from the distillation of sugar cane molasses, concentrated to the 38% of dissolved solid matter, 13.5 kg of concentrated sulfuric acid (specific gravity 1.84 kg/l) are added and, after some minutes of stirring, 34 kg of aqueous ethanol (specific gravity 0.82 kg/l) are added. After about one hour of slow stirring, the thus obtained precipitate is separated by centrifuging by means of a decanter centrifuge, sent to a drying oven operated at 80C under vacuum, and weighed.
33.2 kg of product are so obtained, which is submitted to the chemical analysis, whose results are shown in Table 6, where the concentration values are expressed as % on the weight of the dry product.

~3~3~7 Table 6 Ashes 61.40 Organic matter 38.60 Total nitrogen 0.52 Ammonia nitrogen traces Organic carbon 13.14 Hydrogen 1.78 Potassium 15.47 Magnesium 0.70 Phosphates 0.63 The title of the so obtained potassic saline is therefore: N:P2O5:K2O:MgO = 0.5:0.5:18.5:1.
By integrating this potassic saline, formulations of organo-mineral fertilizers are obtained, which are similar to those shown in the proceeding Examples 1 and 2.

Example 4 In a closed reaction vessel equipped with stirring means, containing 253 kg of vines effluents from the production of citric acid from beet molasses, such vines having been concentrated at a content of 57% of dissolved solids, 14.5 kg of concentrated sulfuric acid (specific gravity 1.84 kg/l) are added and, after some minutes of stirring, 34 kg of aqueous ethanol (specific gravity 0.82 kg/l) are added. After about one hour of stirring, the thus obtained precipitate is separated by centrifuging, by means of a basket centrifuge, sent to a drying oven operated at 80C under vacuum, and weighed. 69.6 kg of product are thus obtained, which is submitted to chemical analysis, whose results are shown as % on the weight of the dry product, in Table 7.

It Table 7 Ashes 39.20 Organic matter 61.80 S Total nitrogen 4,55 Ammonia nitrogen 0.31 Organic carbon 24.90 Hydrogen 3.36 Potassium 11.79 Magnesium 0.43 Phosphates 0.46 The potassic saline thus obtained has therefore a title N:P2O5:K2O:MgO of 4.5:0.3:14.1.
By integrating such potassic saline, formulations are obtained of organo-mineral fertilizers similar to those shown in the proceeding Examples 1 and 2.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A water-soluble solid composition of complex organo-mineral fertilizer, comprising:-(a) a product obtained from the desalting of vinasse from industrial sugar fermentation, the vinasse having a solid content within the range from 35% to 65% by weight, the desalting being carried out using (i) sulphuric acid having a specific gravity in the range from 1.69 to 1.84 Kg/l in a quantity within the range from 1.3 to 1.8 kg per kilogram of potassium in the vinasse, (ii) from 10 to 25 parts by volume, per 100 parts by volume of vinasse, of an organic solvent inert towards the other components, selected from the group consisting of lower alcohols and lower ketones; and (b) at least one organic or inorganic compound, bearer of phosphorous and/or nitrogen;

said composition containing total nitrogen in a quantity of not less than 3% of its weight, with at least 1.5% by weight or organic nitrogen, phosphorous, expressed as P2O5, in a quantity of not less than 4% by weight, potassium, expressed as K2O, in a quantity of not less than 5% by weight, and organic carbon in a quantity of not less than 8% by weight.

2. A composition according to claim 1, wherein the (a) component is obtained by placing the vinasse in contact with the sulphuric acid to form a mixture which is added to the organic solvent followed by separation and drying of the precipitate formed.

3. A composition according to claim 1 or 2, wherein the organic solvent is ethanol.

4. A composition according to claim 1 or 2, wherein the (b) component is selected from the group consisting of urea, nitrates, ammonium salts, superphosphates, phosphoric acid, salts of the phosphoric acid, blood meal and concentrated vinasses.

5. A composition according to claim 1 or 2, wherein the vinasse used to obtain component (a) comes from the industrial fermertation of molasses.

6. A composition according to claim 1 or 2, wherein the vinasse used to obtain component (a) comes from the residue from the production of a substance selected from the group citric acid, glycerine, glutamic acid, lactic acid, butyl alcohol, acetone and antibiotic substances.

7. A composition according to claim 1 or 2, wherein the vinasse has a solid content ranging from 50 to 60% by weight.

8. A composition accordinig to claim 2, wherein the precipitate is dried at a temperature below 130°C.

9. A composition according to claim 1 or 2, wherein component (a) has a potassium titre of about 15%, an organic carbon content ranging from 15 to 25% by weight and a non-ammoniacal nitrogen content ranging from 0.5% to 5% by weight.

10. A composition according to claim 1 or 2, additionally comprising:-(c) a potassium bearing salt.