GB1561136A - Liquid nutrient composition for use in plant fertilizationand in animal feeding - Google Patents

Description

(54) LIQUID NUTRIENT COMPOSITION FOR USE.

IN PLANT FERTILIZATION AND IN ANIMAL FEEDING (71) We, THE UNIVERSITY COURT OF THE UNIVERSITY OF GLASGOW, a British corporate body, of The University, Glasgow, G12, Scotland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The subject of this invention is a liquid nutrient composition for agricultural use, particularly as an additive to animal feed stuffs and as a fertilizer for application to crops and/or soil.

Ruminant animals are usually given diets generally containing grass, hay, silage, straw, root crops and various cereals. The diet may also contain waste by-products from breweries and distilleries and products made from sugar beet. Such a diet is almost always dificient in substances such as nitrogen, calcium, phosphorus and trace elements and vitamins. Because of this it has been the custom to feed animals with supplementary materials. To provide additional nitrogen they have been given for example ground nut, cottonseed, soya bean, linseed and fish and bone meals but these substances are expensive and have largely to be imported into Europe. An alternative source of nitrogen found to be suitable for giving to ruminant animals is urea.This substance has the advantage that is is a highly concentrated source of nitrogen and thus only a small proportion in the feed is required but it has the serious disadvantage that if consumed in excessive amounts it may be fatally toxic to the animal consuming it.

The principal additives generally required in basal diets given to ruminant animals are compounds containing nitrogen, calcium and phosphorus. Sodium chloride and magnesium additions are less generally needed but are nevertheless desirable. Various elements including copper, cobalt, manganese, iron, zinc, selenium and iodine are required in special circumstances in trace amounts. Calcium is normally provided as calcium carbonate and phosphorus as dicalcium phosphate or steamed bone flour (both of which additionally contain calcium). These materials are almost insoluble in water. Magnesium is normally provided as magnesium oxide which is also insoluble. Trace elements are normally provided as their sulphates, and iodine as potassium iodide.

Vitamins, A, D and E are generally required, especially when cattle are housed during the winter.

Heretofore it has been the custom of farmers to buy supplementary materials separately and mix them with the animal feed. Sometimes the materials are given to the animals separately i.e. apart from the feed. This has been recent practice and in fact the tendency has been to place a quantity of the supplementary material on free offer to the animals leaving them to help themselves on the assumption that each animal will take what it needs.

However, all the farmer can control by this method of providing supplementary feed is the total amount required by a group of animals. The applicants have discovered by experiment that the intake of such products is very variable on a day to day basis by each animal.

Consumption is thus not properly controlled. There is also the added disadvantage that urea otherwise so suitabe tends to be unpalatable and the animal is thus not induced to eat its requirement. If the substance is made to be palatable e.g. by the addition of molasses the animal may take too much. Attempts have been made to control the voluntary intake by providing the supplementary material in such a form that the animal must lick it rather than drink it.

Urea mixtures in themselves are unpalatable. Known urea mixtures in liquid form contain about 10% - 15% urea and to overcome the problem of lack of palatibility the urea solution is usually mixed with several times its own weight of molasses. This raises its own problems because it has not been found possible to incorporate an appropriate amount of calcium because of precipitation problems.

It is now the custom to administer the required amount of calcium, common salt and trace elements as a separate substance or separate substances to avoid interaction with other substance.

A liquid nutrient composition for adding to ruminant feed or as a fertilizer should for convenience have the following characteristics as far as possible.

a) It should be concentrated to reduce the quantity to be handled and keep to a minimum the resulting wetness of the actual feed to which the liquid is added.

b) It should have no sediment.

c) It should be free flowing and should be capable of being stored for long periods in fluctuating temperature conditions without forming a precipitate and it should be possible to store it in normal containers and pass it through pumps of normal construction.

d) It should contain as much non-protein nitrogen as possible.

e) It should contain calcium and phosphorus.

f) Include sodium chloride, magnesium, trace elements and vitamins if desired.

g) As an animal feed supplement it should be palatable when mixed with the other feed or feeds to be given to the animal.

h) The ingredients should be readily available and not unduly costly.

These requirements make the use of the urea as the source of nitrogen virtually a necessity. The main alternatives to urea are the ammonium salts but there are unsuitable for several reasons. Firstly, it is not legally possible at the moment to equate nitrogen in the form of ammonia with crude protein. Secondly, most organic ammonium salts such as the lactate, acetate and propionate, contain only about 10% N and are expensive. Thirdly, ammonium sulphate (21% N) cannot be used as it forms a massive precipitate with calcium salts in solution. Fourthly, many ammonium salts are unpalatable and are more potentially toxic than urea. Ammonium phosphates and polyphosphates and other polyphosphates which are water soluble cannot be used because of precipitation in the presence of calciun salts which are an essential constituent of any really effective liquid feed additive.

It will be noted that the first characteristic mentioned is that the substance should be concentrated. Heretofore this has presented an apparently insuperable difficulty to the use of urea in that previously urea could not be made to form an aqueous solution containing more than about 50% urea to water.

The result of this difficulty is that when the known liquids are used as an additive to animal feed in the quantity necessary to provide the desired intake of urea they cause the feed to become undesirably wet. Whether for use as an animal feed or as a fertilizer the high proportion of water present maximizes the bulk to be transported and this keeps transport costs high as well as causing handling difficulties. Another difficulty of the known liquids has been the tendency for precipitation to occur as a result of interaction of the various ingredients.

Phosphoric acid is the most concentrated and suitable form of phosphorus. It is already in liquid form and available at a suitable price. Its acidic nature is important. It has been discovered that urea in the presence of phosphoric acid is less potentially toxic to animals than urea alone or in admixture with dicalcium phosphate. The acidity also enables the calcium and any added trace elements to be kept in solution.

Calcium chloride is the preferred calcium source on the grounds of solubility and cost.

Calcium nitrate (another soluble calcium salt) is toxic to ruminants. Calcium carbonate and calcium sulphate are insoluble. Sodium chloride of the common sodium salts is the preferred source of sodium, as sodium nitrate is toxic and sodium sulphate would form a precipitate with soluble calcium salts.

It may also be desirable to provide some or all of the following substances: (a) Molasses (of a type known to form no precipitate with a calcium solution). Molasses is not necessary in a fertilizer.

(b) Magnesium, copper, cobalt, zinc, iron, selenium and manganese in the form of the chlorides, also potassium iodide (for animal use only).

(c) Vitamins A, D3 and E in liquid form. (Not necessary in a fertilizer).

The purpose of the present invention is to provide a single liquid composition suitable for use as a feed additive or as a soil fertilizer which as a feed additive contains all the substances required to supplement the normal feed constituents of ruminants and which can be intermixed with or sprayed on to the feed material so that the animal will be forced to consume it along with its principal foods, hay straw, silage, fodder, roots, cereals etc. and which as a soil fertilizer contains all the substances required in the fertilization of soil.

The present applicants after extensive experiments, have produced a liquid composition which contains a considerably higher proportion of urea to water than has hitherto been believed possible while also containing if necessary phosphoric acid and other ingredients.

They have also discovered a method of making the composition.

A liquid nutrient composition for use in plant fertilization and in animal feeding according to the invention incorporates at least urea, calcium chloride and water in proportions by weight one to the other, irrespective of the presence or absence of any other substance, which lie in the ranges 38% sCO. (NH2)260%; 0 < CaCl225% and water to 100%, subject to the conditions that for any percentage x of urea in the range 38% to 60%, the percentage being treated as a simple numeral, the maximum percentage of calcium chloride is determined from the equation: maximum percentage CaC12 = 42.27 - 0.455x for any percentage x of urea in the range 38% to 50% the minimum percentage of calcium chloride is determined from the formula: 25D minimum percentage CaC12 > 104.15 - 2.083x and for any percentage x of urea in the range 50% to 60% the minimum percentage of calcium chloride is determined from the formula: minimum percentage CaC12 > 1.50x - 75.00 and that the proportion by weight of urea is greater than the proportion by weight of water.

The basic discovery of the invention is shown in the accompanying graph which is given for explanatory purposes only and is accurate within practical drawing limits. All the proportions represented by the portion of the graph lying above the line A-C-B refer to the proportions by weight of urea, calcium chloride and water which can form a liquid free of undissolved material. Proportions lying within the area of the graph below the line A-C-B produce a liquid in which undissolved material is necessarily present. It will be appreciated of course that the graph includes the known pure urea solutions in water up to the maximum known concentration of about 50% urea to water and the known pure calcium chloride solutions in water up to the maximum known concentration of about 42% calcium chloride to water. These compositions are outside the scope of the present invention.The highest proportion of urea for minimum water is represented by the point C at which the proportion of urea is 60%, the proportion of calcium chloride is 15% and the proportion of water is 25%. In this concentration the urea is present in solution in a proportion to water about two and a half times as much as has been heretofore attainable. As It is the presence of calcium chloride in solution which makes possible the much greater solubility of urea it will be seen that the urea/CaCl2/H2O composition of the invention lies only within the portion of the part of the graph which is contained within the area bounded by the portion ADC.

Examples of use of the equations are given below.

Urea 60% (upper limit or urea) gives maximum CaCl2 15.0% and the equation for minimum Cacti2 with 60% urea gives also a percentage of 15.0%. This agrees with point C on the graph and shows that for 60% urea it is necessary to use 15% CaCl2.

38% of urea (lower limit) the maximum Cacti2 usable is 25.0% and the minimum is also 25.0%. This corresponds with the point D on the graph and shows that at the lowest limit of 38% urea it is necessary to use 25% CaCl,.

The proportion of CaCI2 has a range of values when used with urea at intermediate percentages e.g. at 45% urea, the maximum percentage of Call, is 21.8% and the minimum percentage is 10.4% i.e. any percentage of CaCI2 between 10.4% and 21.8% can be used with 45% urea to give the effect of the invention.

In all cases there is also present water to 100% eit r as free water or as free water and combined water. As is explained later in the specificatt other substances may be added to the mixture but they are added as additions to the 10v 7s composition containing urea, CaCI2 and water.

The liquid nutrient composition according to the invention may also contain phosphoric acid. The amount of phosphoric acid which can be present without formation of a precipitate has been found to be dependent on the amount of calcium chloride in the urea/CaCl2/H2O composition and also the amount of urea in the urea/CaCl2/H2O composition. On a parts by weight basis the maximum amount of phosphoric acid which can be present without precipitation in,any specific urea/CaCl2/H2O composition lying within the scope of the invention is given by the following equation.

p = 90 antilog (2.63 - 0.1353 (us)05) . . . (i) where p represents the maximum number of parts by weight to an accuracy of i 5% of H3PO4 which can be added to 1 part by weight of a urea/CaCl2/H2O composition of specific proportions.

c is the percentage of Cacti2 (w/w) contained in the same specific composition inserted in the equation as a simple numeral, e.g. 12.5% is inserted as 12.5.

u is the percentage urea (w/w) contained in the same specific composition also inserted as a numeral.

z is a factor representing the percentage phosphoric acid by weight in the additive expressed as a simple numeral. This factor takes account of the fact that phosphoric acid almost invariably contains some water.

From a practical point of view the formula is applied particularly to urea/CaCl2/H2O compositions in which the Cacti2 is present in the proportion w/w 5%6CaCl2S21%.

This is because with proportions of Cacti2 between 21% and 25% the amount of H3PO4 which can be added ceases to have any practical usefulness and with proportions of Cacti2 less than 5% the graph of the equation becomes asymptotic showing proportions of H3PO4 approaching infinity.

On a percentage by weight basis the maximum amount of phosphoric acid which may be present in a H3PO4/urea/CaCl2/H20 composition is given by the following formula: q = 90 antilog (1.8782 - 1.5652 u1c1 x 10-3) . . . (ii) where q represents the maximum percentage to an accuracy of + 5% of H3PO4 which can be present in a given weight of a H3PO4/urea/CaCl2/H2O composition of specific proportions.

ul and cl are the percentages by weight of urea and Cacti respectively in the H3PO4/urea/CaCl2/H20 composition.

z is a factor representing the percentage phosphoric acid by weight in the additive expressed as a simple numeral. This factor takes account of the fact that phosphoric acid almost invariably contains some water.

Equation (ii) is useful where it is desired to provide a composition containing given proportions of urea, Cacti2 and phosphoric acid. By solving equation (ii) for the particular values of ul and cl in the given composition it becomes at once apparent whether the desired proportion of phosphoric acid can be present without precipitation. If it is found from the equation (ii) that the amount of phosphoric acid proposed is too great it may be possible to accommodate that proportion of phosphoric acid by adjusting the amount of urea and CaCI2 within the limits of the present invention.

The phosphoric acid may be added subsequent to the formation of the urea/CaCl2/H2O composition or may be added during the formation of the urea/CaCl2/H2O composition.

Example I A completely liquid stable urea/CaCl2/H2O composition was made containing 10% calcium chloride 55% urea and 35% water by weight. The proportion of urea to water is thus 55/35 i.e. higher than the maximum 50/50 proportion which has been heretofore obtainable with urea and water alone.

Example II A composition was made containing Caul2, urea and water in the same relative proportions as in Example I, i.e. 10/55/35 and there was added 0.28 part of 90% phosphoric acid to each part of the said composition. There was obtained a completely stable composition free of precipitation and containing by weight 19.7% phosphoric acid (anhydrous), 7.8% calcium chloride, 43.0% urea and the remainder water. In this composition the proportion of urea to water is 43.0/29.5.

The graph actually shows the conditions prevailing at a temperature of 15"C. There are slight variations at other temperatures normally experienced but the ranges of proportions quoted for the constituents of the composition of the invention remain true, within the usual slight variations which inevitably occur when making up such compositions under normal manufacturing conditions, for all temperatures normally experienced.

The calcium chloride may be used in the anhydrous form or in the hydrated form. It will of course be understood that if the CaC12 is used in the hydrated form a corresponding reduction in the quantity of water making up the complete bulk of the urea/CaCl2/H2O composition will be made so that the total water including the water of crystallization of the hydrated material still lies within the proportions referred to as being within the scope of the invention.

Trace elements such as magnesium, manganese, copper, cobalt, iron and zinc for example in the form of chlorides of these substances may be added in amounts preferably not exceeding 1% by weight. Also potassium iodide may be added in a small proportion.

Sodium chloride may also be added.

Molasses in the proportion of 1% to 15% by weight may be included in the composition.

Vitamins A, D and E where necessary are preferably added in liquid form.

In practice the liquid composition according to the invention provides a completely stable liquid without precipitate which contains urea in a proportion to the water content of the composition greater than has been heretofore attainable. When used as a feed additive this ensures that the feed is wetted to the minimum extent. Also, whether as a feed additive or a fertilizer the low water content contributes to lowered transport costs and reduced handling difficulties. This desirable and heretofore unobtainable effect has been produced by the proportions of the materials used and also by the manner in which they are mixed.

Heretofore all attempts to incorporate calcium in a liquid supplement for ruminant feed have failed because previously the calcium had always precipitated and in fact many authorities have stated that calcium should always be added separately to the dry feed.

Attempts have been made to incorporate calcium in a liquid feed as it is most desirable that a liquid supplement should supply everything that is needed by an animal on a day to day basis. The previous attempts to incorporate calcium have been aimed at providing calcium in the form of a suspension. Such a type of product is most undesirable where long storage times and varying conditions are likely to be met with because of the great likelihood of the sedimentation of calcium compounds. Sedimentation in liquid fertilizers causes serious difficulty with blocking of nozzles during spraying of the fertilizer. The composition of the invention completely eliminates this difficulty.

Urea administered in an uncontrolled manner may prove fatally toxic to animals and in addition when given alone it has an unpalatable taste. The liquid composition according to the invention can, however, contain a high proportion of urea because it has been discovered that urea in the presence of phosphoric acid is less potentially toxic to animals.

Also the comparatively high concentration of urea in the composition makes it possible to reduce the quantity of the additive put into the animals'main feed so that its comparative unpalatibility is reduced and in fact it has been found that the taste of the normal main feed of the animals is usually sufficient to eliminate the lack of palatability of the composition without the addition of expensive molasses.

In the specification all references to the various substances forming the composition may be taken as being the commercial quality of these substances although the invention also applies to the use of substances of greater purity than commercial quality. In this connection it may be remarked that where phosphoric acid in particular is used a common commercial quality is a 90% solution of phosphoric acid i.e. the phosphoric acid actually used consists of 90% H2PO4 and 10% HO. Other concentrations of phosphoric acid are, however, obtainable and it is emphasized that where it is intended to make a nutrient composition containing phosphoric acid any water content of the phosphoric acid is to be taken into account in the calculations relating to the urea/CaCl2/water protion of the composition.

WHAT WE CLAIM IS: 1. A liquid nutrient composition for use in plant fertilization and in animal feeding incorporating urea, calcium chloride and water in proportions by weight one to the other, irrespective of the presence or absence of any additional substance, which lie in the ranges 38% 6CO.(NH2)2660%; O > CaCl225% and water to 100%, subject to the conditions that for any percent x of urea in the range 38% to 60%, the percentage being treated as a simple numeral, the maximum percentage of calcium chloride is determined from the equation: maximum percentage CaCI2 = 42.27 - 0.455x, for any percentage x of urea in the range 38% to 50% the minimum percentage of calcium chloride is determined from the formula:: 25 minimum percentage CaCI2 > 104.15 - 2.083x and for any percentage x of urea in the range 50% to 60% the minimum percentage of calcium chloride is determined from the formula: minimum percentage CaCI2 > 1.50x - 75.00 and that the proportion by weight of urea is greater than the proportion by weight of water.

2. A liquid nutrient composition as claimed in claim 1 containing phosphoric acid as an additive in which the amount of phosphoric acid present as the additive lies in the range: O < p690 antilog (2.63 - 0.1353 (us) .5) where p represents the maximum number of parts by weight to an accuracy of + 5% of H3PO4 to 1 part by weight of a urea/CaCl2/H2O composition of specific proportions, c is the percentage of CaCl2 (w/w) contained in the same specific composition inserted in the equation as a simple numeral, e.g. 12.5% is inserted as 12.5, u is the percentage urea (w/w) contained in the same specific composition also inserted as a numeral, z is a factor representing the percentage phosphoric acid by weight in the additive expressed as a simple numeral.

3. A liquid nutrient composition as claimed in claim 1 containing phosphoric acid as an additive in which the amount of phosphoric acid present as the additive lies in the range:

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (4)

**WARNING** start of CLMS field may overlap end of DESC **. In practice the liquid composition according to the invention provides a completely stable liquid without precipitate which contains urea in a proportion to the water content of the composition greater than has been heretofore attainable. When used as a feed additive this ensures that the feed is wetted to the minimum extent. Also, whether as a feed additive or a fertilizer the low water content contributes to lowered transport costs and reduced handling difficulties. This desirable and heretofore unobtainable effect has been produced by the proportions of the materials used and also by the manner in which they are mixed. Heretofore all attempts to incorporate calcium in a liquid supplement for ruminant feed have failed because previously the calcium had always precipitated and in fact many authorities have stated that calcium should always be added separately to the dry feed. Attempts have been made to incorporate calcium in a liquid feed as it is most desirable that a liquid supplement should supply everything that is needed by an animal on a day to day basis. The previous attempts to incorporate calcium have been aimed at providing calcium in the form of a suspension. Such a type of product is most undesirable where long storage times and varying conditions are likely to be met with because of the great likelihood of the sedimentation of calcium compounds. Sedimentation in liquid fertilizers causes serious difficulty with blocking of nozzles during spraying of the fertilizer. The composition of the invention completely eliminates this difficulty. Urea administered in an uncontrolled manner may prove fatally toxic to animals and in addition when given alone it has an unpalatable taste. The liquid composition according to the invention can, however, contain a high proportion of urea because it has been discovered that urea in the presence of phosphoric acid is less potentially toxic to animals. Also the comparatively high concentration of urea in the composition makes it possible to reduce the quantity of the additive put into the animals'main feed so that its comparative unpalatibility is reduced and in fact it has been found that the taste of the normal main feed of the animals is usually sufficient to eliminate the lack of palatability of the composition without the addition of expensive molasses. In the specification all references to the various substances forming the composition may be taken as being the commercial quality of these substances although the invention also applies to the use of substances of greater purity than commercial quality. In this connection it may be remarked that where phosphoric acid in particular is used a common commercial quality is a 90% solution of phosphoric acid i.e. the phosphoric acid actually used consists of 90% H2PO4 and 10% HO. Other concentrations of phosphoric acid are, however, obtainable and it is emphasized that where it is intended to make a nutrient composition containing phosphoric acid any water content of the phosphoric acid is to be taken into account in the calculations relating to the urea/CaCl2/water protion of the composition. WHAT WE CLAIM IS:

1. A liquid nutrient composition for use in plant fertilization and in animal feeding incorporating urea, calcium chloride and water in proportions by weight one to the other, irrespective of the presence or absence of any additional substance, which lie in the ranges 38% 6CO.(NH2)2660%; O > CaCl225% and water to 100%, subject to the conditions that for any percent x of urea in the range 38% to 60%, the percentage being treated as a simple numeral, the maximum percentage of calcium chloride is determined from the equation: maximum percentage CaCI2 = 42.27 - 0.455x, for any percentage x of urea in the range 38% to 50% the minimum percentage of calcium chloride is determined from the formula:: 25 minimum percentage CaCI2 > 104.15 - 2.083x and for any percentage x of urea in the range 50% to 60% the minimum percentage of calcium chloride is determined from the formula: minimum percentage CaCI2 > 1.50x - 75.00 and that the proportion by weight of urea is greater than the proportion by weight of water.

2. A liquid nutrient composition as claimed in claim 1 containing phosphoric acid as an additive in which the amount of phosphoric acid present as the additive lies in the range: O < p690 antilog (2.63 - 0.1353 (us) .5) where p represents the maximum number of parts by weight to an accuracy of + 5% of H3PO4 to 1 part by weight of a urea/CaCl2/H2O composition of specific proportions, c is the percentage of CaCl2 (w/w) contained in the same specific composition inserted in the equation as a simple numeral, e.g.

12.5% is inserted as 12.5, u is the percentage urea (w/w) contained in the same specific composition also inserted as a numeral, z is a factor representing the percentage phosphoric acid by weight in the additive expressed as a simple numeral.

3. A liquid nutrient composition as claimed in claim 1 containing phosphoric acid as an additive in which the amount of phosphoric acid present as the additive lies in the range:

O < qA20antilog (1.8782 - 1.5652 u1c1 x 10-3) where q represents the maximum percentage to an accuracy of t 5% of H3PO4 in a given weight of a H3PO4/urea/CaCl21 H2O composition of specific proportions, ul and c1 are the percentages by weight of urea and CaC12 respectively in the H3PO4/urea/CaCl21H2O composition, z is a factor representing the percentage of pure phosphoric acid by weight in the additive expressed as a simple numeral.

4. A liquid nutrient composition substantially as described and claimed in any of claims 1 or 2 or 3.