WO1991003167A1

WO1991003167A1 - Process for producing a mineral animal feed supplement

Info

Publication number: WO1991003167A1
Application number: PCT/US1990/004236
Authority: WO
Inventors: Tim D. Welcomer; David A. Richie
Original assignee: Pitman-Moore, Inc.
Priority date: 1989-09-06
Filing date: 1990-07-30
Publication date: 1991-03-21
Also published as: AU6141390A

Abstract

A process for simply and inexpensively producing a mineral animal feed supplement and animal feeds compositions containing the mineral animal feed supplement by reacting phosphoric acid, limestone and trona ore at room temperature is disclosed.

Description

PROCESS FOR PRODUCING A MINERAL ANIMAL FEED SUPPLEMENT

This invention relates generally to a process for producing a mineral animal feed supplement and animal feeds compositions containing the mineral animal feed supplement. In particular, the present invention relates to a process for simply and inexpensively- producing a mineral animal feed supplement using phosphoric acid, a calcium source and a sodium source.

Background of the Invention Most animals, particularly cattle, swine and poultry, are fed controlled diets to maximize their growth rate, feed efficiency or productivity. Feeds developed for this purpose are known to be deficient in some minerals; mineral supplements must be added to the animal's diet to insure the the animal's health and development. In particular, these mineral supplements must contain phosphorus, calcium and sodium in a form and in amounts which can readily be used by the animal as a nutrient. The mineral animal feed supplements currently in use often contain phosphorus, calcium and sodium in a form and in amounts suitable to insure the health of the animal. However, the processes used to produce available mineral animal feed supplements are complicated and difficult and/or are expensive. For example, British Patent 1 257 691 discloses a mineral animal feed supplement consisting of calcium sodium ortho phosphate prepared by heating di-calcium phosphate with sodium carbonate at a temperature of from about 200-1200°C. U.S. Patent No. 3,391,416 discloses a calcium-sodium-phosphate feed supplement produced by heating calcium oxide, sodium oxide and P₂0₅ at a temperature of from about 600-1000°C. U.S. Patent No. 3,851,086 discloses a feed supplement produced by heating triple superphosphate or a combination of phosphate rock and aphosphoric acid, sodium hydroxide and calcium carbonate at a temperature of at least about 2250°F.

All these available methods involve high temperature processes which are difficult to control and require complicated equipment to accomplish; the resulting mineral animal feed supplement is therefore relatively expensive. A simple and inexpensive process for producing mineral animal feed supplements is therefore needed.

Summary of the Invention It is, therefore, an object of the present invention to provide a process for simply and inexpensively producing a mineral animal feed supplement containing phosphorous, calcium and sodium. It is another object of the present invention to provide an animal feed composition containing the mineral animal feed supplement.

These and other objects are achieved by reacting phosphoric acid, calcium carbonate, and a sodium source selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and trona ore. The reactants are simply mixed, typically in a pug mill or granulator, and allowed to react. The reaction proceeds spontaneously at room temperature; no heat or other form of energy is required to initiate and sustain the reaction. The resulting product is dried to produce a solid mineral animal feed supplement containing the desired amounts of phosphorus, calcium, and sodium. The dried product is processed to produce a mineral animal feed supplement suitable for preparing an animal feed composition containing the supplement. The processed supplement is admixed with or applied to an animal's feed to supplement dietary phosphorus, calcium and sodium.

Other objects, advantages, and novel features of the present invention will become apparent from the following detailed description of the invention.

Detailed Description of the Invention According to the present invention, a process is provided for simply and inexpensively producing a mineral animal feed supplement containing phosphorous, calcium and sodium. The process comprises reacting phosphoric acid, calcium carbonate, and a sodium source selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and trona ore. The reactants are simply mixed and allowed to react. The reaction proceeds spontaneously at room temperature; no heat or other form of energy is required to initiate and sustain the reaction. The resulting product is dried to produce a mineral animal feed supplement containing the desired amounts of phosphorus, calcium, and sodium.

Phosphoric acid is available commercially and can be obtained from any suitable source; the phosphoric acid can be purchased as a reagent grade material but preferably is the run-of-plant (ROP) product from a wet-process production facility. Preferably, the phosphoric acid used to make feed supplements is defluorinated phosphoric acid. The phosphoric acid solution useful in the present invention should have a concentration of from about 30-60% P₂0₅, preferably about 50% P₂0₅.

Calcium carbonate is available commercially and can be obtained from any suitable source; calcium carbonate can be purchased in the purified form or preferably is obtained by reacting limestone in the present process. The limestone should contain from about 30-45% calcium, preferably about 40% calcium.

Sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and trona ore are available commercially and can be obtained from any suitable source. Sodium carbonate, sodium bicarbonate and sodium sesquicarbonate can be purchased in the purified form; preferably sodium for the reaction is obtained by using trona ore in the present process. The trona ore should contain from about 20-35% sodium, preferably about 30% sodium.

The process of the present invention preferably comprises reacting from about 6.5 moles of P₂0₅ with from about 8.1 moles of calcium carbonate and from about 4.0 moles of sodium from a source selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and trona ore. Obviously, the amount of sodium compound required will depend upon the compound selected and, for trona ore, the percent sodium in the ore. Similarly, when limestone is used as a calcium carbonate source, the amount of limestone required will depend upon the percent calcium in the ore.

In one embodiment of the present invention, about 9 parts by weight of a 50% P₂0₅ phosphoric acid solution is reacted with about 5 parts by weight of calcium carbonate and about 1 part by weight of sodium carbonate. Typically, a mixture of 1:5 sodium carbonate:calcium carbonate is slowly added to a phosphoric acid solution while mixing.

In the most preferred embodiment, about 27 parts by weight of a ~38% P₂0₅ phosphoric acid solution is reacted with about 9 parts by weight limestone containing about 38% calcium and 4 parts by weight trona ore containing about 27% sodium.

The skilled artisan can easily calculate the amount of reactants required to produce the mineral animal feed supplement according to the process of the present invention given their composition and concentration. Such a typical formula for calculating reactant amounts to produce 100 grams (g) of product is given as follows: g Na Compound = 500 ÷ % Na in the Na Compound g Limestone = 1760 ÷ % Ca in the Limestone g Phosphoric Acid (PA) = 5000 ÷ % P₂0₅ in the PA The mineral animal feed supplement of the process of the present invention can easily be formulated into a form suitable for preparing an animal feed composition, typically using a pug mill or granulator. Many such methods are known to skilled artisans. The mineral animal feed supplement produced according to the process of the present invention is administered orally to an animal in the animal's feed. For example, the mineral animal feed supplement can be blended with ordinary feed compositions, sprinkled on the animals feed, or fed free choice.

In the preferred embodiment, the mineral animal feed supplement is administered to the animal by feeding the animal a feed composition containing the supplement in amounts sufficient to supplement the animal's diet with sodium, calcium, and phosphorus at recommended levels.

A feed composition may be prepared containing the mineral animal feed supplement and the usual nutritionally-balanced feed containing quantities of carbohydrates, fats, proteins, vitamins and other minerals in accordance with the present invention. Some of the usual dietary elements included in feed compositions are grains, such as ground grain and grain byproducts, swine protein substances, such as those found in fish meal and meat scraps, vegetable proteins, like soybean oil meal or peanut oil meal; and vitamins and vitamin-containing materials, e.g., vitamin A and D mixtures, riboflavin supplements and other vitamin B complex members. A type of conventional feed material for use with swine includes corn and soybean meal together with supplementary vitamins, vitamin-containing substances, and other minerals if desired. An example of a well known feed composition which may be useful in the present invention is disclosed in U.S. Patent No. 4,320,116 (basic ingredients for feed compositions for swine, piglets, and other swines), incorporated herein by reference. Many other such feed compositions are well known to those skilled in the art.

Although the amount of the mineral animal feed supplement an animal requires varies according to the type, age, size, and character of the particular animal, the mineral animal feed supplement is typically fed to the animal in amounts sufficient to supply from about 0.1-0.4% dietary sodium, preferably about 0.2%, from about 0.3-1.4% dietary calcium, preferably about 1%, and from about' 0.4-0.9% dietary phosphorous, preferably about 0.5%.

In the preferred embodiment, the mineral animal feed supplement is admixed with the animal's feed in amounts sufficient to supply the necessary dietary requirements, typically by preparing a feed composition containing from about 1-10% of the mineral animal feed supplement, preferably about 1-3% of the mineral animal feed supplement. This is conveniently accomplished by applying to or admixed with the feed from about 20-60 pounds of supplement per ton of feed.

The invention having been generally described, the following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims to follow in any manner.

Example 1 A mineral animal feed supplement was produced by weighing 47.78 grams (g) of 51.8% P₂0₅ defluorinated phosphoric acid (prepared by mixing appropriate amounts of reagent grade concentrated defluorinated phosphoric acid with deionized water) into a 400 milliliter (ml) glass beaker. A mixture of 24.07 g of reagent grade calcium carbonate and 6.39 g of reagent grade sodium carbonate was added in small increments to the acid in the beaker and mixed manually with a glass rod. At the beginning of the reaction, the mixture had the consistency of a thick paste and the continual

"popping" of the release of carbon dioxide was heard. After a few minutes of stirring, the mixture became syrupy and the "popping" subsided. This syrupy reaction product was dried overnight at 105°C to produce a hard, brittle product.

The product was evaluated for phosphorus, calcium, and sodium content and was evaluated using x-ray diffraction (XRD) analysis. The analytical results were: P - 23.4%, Ca - 18.4%, Na - 7.27%, XRD - major CaHP0₄ and minor NaH₂P0₄.

Example 2 A mineral animal feed supplement was produced by weighing 34.78 g of 51.8% P₂0₅ defluorinated phosphoric acid (prepared by mixing appropriate amounts of reagent grade concentrated defluorinated phosphoric acid with deionized water) into a 400 ml glass beaker. A mixture of 18.17 g of reagent grade calcium carbonate and 3.85 g of reagent grade sodium carbonate was added in small increments to the acid in the beaker and mixed manually with a glass rod. At the beginning of the reaction, the mixture had the consistency of a thick paste and the continual "popping" of the release of carbon dioxide was heard. After a few minutes of stirring, the mixture became syrupy and the "popping" subsided. This syrupy reaction product was dried overnight at 105°C to produce a hard, brittle product.

The product was evaluated for phosphorus, calcium, and sodium content. The analytical results were: P - 23.1%, Ca - 20.6%, and Na - 5.38%.

Example 3 The hygroscopic nature of the product from Example 2 was determined by (1) generating an atmosphere of 90% relative humidity in a closed desiccator by mixing 200 milliliters (mis) of reagent grade concentrated sulfuric acid with 800 mis of deionized water in the bottom of the desiccator, (2) placing a platform inside above the solution, (3) placing an open glass weighing dish containing 10 g of sample on the platform, (4) and sealing the desiccator. The sample dish was removed periodically from the closed desiccator and weighed. Afterwards, the dish was returned to the desiccator until the next weighing. This weighing procedure continued for 10 days.

The total increase in the weight of the sample in the atmosphere of 90% relative humidity over the 10-day period was 14.25%. The sample did not gain more weight upon further exposure to the high humidity, so the test was ceased. The weight gain was sufficiently high to identify the sample as being hygroscopic.

The results from Examples 1-3 show that on a laboratory scale a mineral animal feed supplement containing phosphorus, calcium, and sodium can be simply and inexpensively produced.

Example 4 A mineral animal feed supplement was made from commercial reagents, i.e. limestone, Trona ore and Run-of-Plant (ROP) defluorinated phosphoric acid, obtained from a phosphoric acid production plant at New Wales, FL. To determine the proper amount of each reagent needed to make a calcium phosphate product containing 5% sodium, the limestone was analyzed for calcium, the trona ore for sodium and the ROP phosphoric acid for phosphorus. To alleviate the difficulties associated with pumping a highly viscous fluid at the plant, the ROP acid is diluted with water to a P₂0₅ concentration range of 38-40%. Therefore, the ROP acid used in this study was diluted with deionized water and the diluted acid was analyzed for phosphorus. The results of the analysis of the reagents are given in Table 1. Example 5 A mineral animal feed supplement was produced by weighing 80.27 g of 38.3% P₂0₅ defluorinated phosphoric acid into a 400 ml glass beaker. A mixture of 28.42 g of limestone and 9.07 g of Trona ore was added in small increments to the acid in the beaker and mixed manually with a glass rod. At the beginning of the reaction, the mixture had the consistency of a thick paste and the continual "popping" of the release of carbon dioxide was heard. After a few minutes of stirring, the mixture became syrupy and the "popping" subsided. This syrupy reaction product was dried overnight at 120°C to produce a hard, brittle product.

The product was evaluated for phosphorus, calcium, fluoride and sodium content and was evaluated using x-ray diffraction (XRD) analysis. The analytical results are shown in Tables 2 and 3 for Product 1. The mean of the results given in Table 2 are shown in Table 4. Example 6

A mineral animal feed supplement was produced by weighing 81.41 g of 38% P₂0₅ defluorinated phosphoric acid into a 400 ml glass beaker. A mixture of 25.57 g of limestone and 13.61 g of Trona ore was added in small increments to the acid in the beaker and mixed manually with a glass rod. At the beginning of the reaction, the mixture had the consistency of a thick paste and the continual "popping" of the release of carbon dioxide was heard. After a few minutes of stirring, the mixture became syrupy and the "popping" subsided. This syrupy reaction product was dried overnight at 120°C to produce a hard, brittle product.

The product was evaluated for phosphorus, calcium, fluoride and sodium content and was evaluated using x-ray diffraction (XRD) analysis. The analytical results are shown in Tables 2 and 3 for Product 2. The mean of the results given in Table 2 are shown in Table 4. Example 7

The hygroscopic nature of the product from Examples 5 and 6 were determined as described in Example 3 for atmospheres of 60% and 90% relative humidity. The 60% humidity environment was generated by mixing 400 mis of reagent grade concentrated sulfuric acid with 600 mis of deionized water in the bottom of a desiccator, placing a platform inside above the solution, placing an open glass weighing dish containing 5 g of sample on the platform and sealing the desiccator. The 90% humidity environment was generated similarly except 200 mis of acid was mixed with 800 mis of water. The sample dishes were removed periodically from the closed desiccators and weighed. Afterwards the dishes were returned to the desiccators until the next weighing. This weighing procedure continued for seven days.

The total increase in the weights of the samples in the atmospheres of 60% and 90% relative humidity over the 7-day period is reported in Table 5. Referring to Table 5, the total increase in the weight of the sample in the atmosphere of 60% relative humidity over the 7-day period was less than 1%. The sample did not gain more weight upon further exposure to the high humidity, so the test was ceased. The total increase in the weight of the sample in the atmosphere of 90% relative humidity over the 7-day period was 14.2%. The sample did not gain more weight upon further exposure to the high humidity, so the test was ceased. The weight gain was sufficiently high to identify the sample as being hygroscopic.

Example 8 A product containing approximately 5% sodium was made by blending the proper amounts of Products 1 and 2 from Examples 5 and 6, respectively. Calculations which used the results in Table 4 indicated that two parts of Product 1 mixed with three parts of Product 2 would yield a final product with the desired concentration of sodium. The required amounts of the two products were weighed alternately in 1 g increments into a glass sample vial. The vial was capped, then alternately rolled and shaken to thoroughly mix the sample. Two separate samplings of the mixture were analyzed for sodium, calcium and phosphorus. The results are reported in Table 6.

Referring to Table 6, a product containing about 5% sodium can be produced by mixing products produced by the above process. A product containing about 5% sodium is desirable since this is the concentration generally considered useful for preparing in animal feeds.

The theoretical amounts of limestone and trona ore, which when mixed with the same amount of acid used to produce the low and high sodium products would yield a product with elemental concentrations approximating those in Table 6 (about 5% sodium), were calculated from the amounts reported in Examples 5 and 6 and the percentage of each of the two products used to make the blended product using the formula: (Product 1 x 0.4) + (Product 2 x 0.6) = theoretical weight. The calculations were:

Limestone: (28.42 g x 0.4) + (25.57 g x 0.6) = 26.71 g Trona Ore: ( 9.07 g x 0.4) + (13.61 g x 0.6) = 11.79 g Therefore, reacting 26.71 g of limestone and 11.79 g of trona ore with approximately 80 g of acid should yield the desired product.

The results from Examples 4-8 show that a calcium phosphate mineral animal feed supplement containing about 5% sodium can be simply and inexpensively produced from the reaction of limestone, trona ore and diluted ROP defluorinated phosphoric acid.

Obviously many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

Table 1

Trona Ore % Na Limestone % Ca 27.6 38.3

ROP % Phosphoric Acid Diluted ROP % Phosphoric Acid 55.0 as P₂0₅ 38.3 as P₂0₅

- not determined

Claims

WHAT IS CLAIMED IS:

1. A process for producing a mineral animal feed supplement containing phosphorous, calcium and sodium, comprising: reacting phosphoric acid, calcium carbonate, and a sodium source selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and trona ore.

2. The process of Claim 1 wherein phosphoric acid is reacted with limestone and trona ore.

3. The process of Claim 2 wherein a 38% P₂0₅ phosphoric acid solution is reacted with limestone containing about 38% calcium and trona ore containing about 27% sodium. . The process of Claim 1 which comprises reacting from about 6.5 moles of P₂0₅ with from about 8.1 moles of calcium carbonate and from about

4.0 moles of sodium from a source selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and trona ore.

5. The process of Claim 1 wherein a 50% P₂0₅ phosphoric acid solution is reacted with calcium carbonate and sodium carbonate in a 9:5:1 ratio by weight.

6. The process of Claim 1 wherein the phosphoric acid is defluorinated phosphoric acid.

7. The mineral animal feed supplement of the process of Claim 6.

8. The mineral animal feed supplement of Claim 7 containing sufficient phosphorous, calcium and sodium to supply from about 0.1-0.4% dietary sodium, from about 0.3-1.4% dietary calcium, and from about 0.4-0.9% dietary phosphorous.

9. The mineral animal feed supplement of the process of Claim 1.

10. The mineral animal feed supplement of Claim 9 containing sufficient phosphorous, calcium and sodium to supply from about 0.1-0.4% dietary sodium, from about 0.3-1.4% dietary calcium, and from about 0.4-0.9% dietary phosphorous.

11. An animal feed composition, comprising: a nutritionally balanced feed; and the mineral animal feed supplement of the process of Claim 1.

12. The feed composition of Claim 11 containing from about 1-10% of the mineral animal feed supplement.

13. The feed composition of Claim 12 wherein the mineral animal feed supplement is applied to or admixed with the feed in amounts of from about 20-60 pounds per ton of feed.

14. The feed composition of Claim 11 wherein the mineral animal feed supplement is the mineral animal feed supplement of the process of Claim 6.