ACID DEFLUORINATION FOR ANIMAL FEEDS By Andrea C, Perkins Senior Process Engineer IMC Fertilizer, Inc. New Wales Operations Mulberry, Florida Presented at the American Institute of Chemical Engineers Central Florida Section Annual Clearwater Meeting May 28, 1988ACID DEFLUORINATION FOR ANIMAL FEEDS INTRODUCTION IMC Fertilizer, Inc., New Wales Operations, is the largest single site phosphate complex in the United States. From raw materials of phosphate rock, sulfur, limestone, soda ash and ammonia the plant produces six fertilizer products, six animal feed products and uranium oxide as a by-product. Pitman-Moore, Inc., a wholly owned subsidiary of IMC is responsible for the production of animal feeds and health products. The phosphate based animal feed products are produced at the New Wales complex which is operated by IMc Fertilizer, Inc. Phosphorus and calcium are needed in animals for the formation and composition of the bones, teeth and muscles. Normally, animals get their nutrients from plants; but in recent years the nutrients are supplemented by the farmer to help in developing the animals quickly. An ideal source of phosphorus is phosphate rock, and the majority of the phosphate based animal feed supplements are made from phosphoric acid, zi Phosphoric acid produced by the wet process method generally contains fluoride compounds in excess of what is considered suitable for animal consumption. Small amounts of fluoride may be beneficial for the animals' development. However, the ingestion of excessive fluorides can cause poor development of the skeleton and teeth, resulting in brittle bones and lameness. Excessive tooth wear, a reduction in weight gain and milk production due to reduced eating and drinking of water are other problems that can occur. Feed-grade phosphates must contain no more than 1 pars of fluorine to 100 parts of phosphorus (P/F=100). Most states require the minimum ratio of phosphorus to fluorine (P/F) in animal feed products to be 100. However, some states require an even higher minimum ratio of 17 Therefore, for the phosphoric acid produced by the wet Process to be used in the production of animal feeds, Gefluorination is necessary. Two different methods of defluorination exist at New Wales. Rotary kilns are utilized for defluorination in producing one of the products. All the other products are produced by steam stripping the phosphoric acid, This paper will discuss the steam stripping process.The animal feed granulation plants at New Wales produce calcium and ammonium phosphate products. They produce five different dry products, and a defluorinated liquid phosphate. CHEMISTRY In Florida rock there is about 3-4% fluorine present after beneficiation, The fluorine is present in the rock as calcium fluoride, calcium fluosilicate, and calcium phosphate fluoride complexes. When the rock is reacted with sulfuric acid in the Phosphoric Acid plant, hydrogen fluoride (HF) and silicon tetrafluoride (Sify) are volatilized as shown in equations (1), (2) and (3). Cary + H2S0, -----> CaS04 + 2HF a Casife + H2S04 -----> Caso, + HySirg (2) HySikg <---> SIP y + 2H a) Some of the fluorine remains in the phosphoric acid as hydrogen fluoride (HF), as fluosilicic acid (HySiF,g), as fluosilicate salts (especially sodium and potassidm), and as metal fluoride complexes (especially aluminum and iron). The stripping of the fluorine from the acid is more easily attained when the fluorine is present in the silicon tetra fluoride form, Silicon tetrafluoride is more volatile than hydrogen fluoride, Silicon dioxide is added to the phosphoric acid to allow the chemical reactions necessary for producing the silicon tetrafluoride. Equations (4) — (8) show the primary reactions that occur wher excess silica is present in the phosphoric acid. 2H2SiFg + Sic, 3SiPy + 2H20 (4) 4HP + Sio, Sify + 2H20 (5) 2Na2SiPg + Sid, 38iFy + 2Na20 (6) 2K2SiFg + Sid, 3SiFy + 2K20 7) 4AlF3 + 35102 -------> 38iFy + 2A1203 (8) Equations (4) and (5) occur very rapidly, and the silicon tetrafluoride is evolved. However, the fluorine present in the acid as fluosilicates and metal complexes, as shown in Equations (6), (7) and (8), reacts slowly, requiring heat and time to occur.Figure 1 shows the solubility curves for sodium and potassium fluosilicates in phosphoric acid (1). The solubility of sodium fluosilicate decreases with increasing P205 strength, and its lowest level appears to be in the 55% strength acid. This is one of the factors that affects the slow reaction rate because the sodium fluosilicate has to be soluble to react with the silicon dioxide. The solubility of potassium fluosilicate in 55% acid is higher than sodium fluosilicate, Unfortunately, there is more sodium than potassium present in the phosphoric acid, and so more sodium fluosilicates are formed. The presence of impurities in the acid affects the form in which the fluorine is present. It appears that the higher the impurity levels, the higher the fluorine level. The worst culprit is aluminum, High levels of dissolved aluminum present in the phosphoric acid can cause various complexes of the fluorine to form such as chukhrovite, Ca4so4(Alf¢)(Sifg)(OH).12H20, and cryolite (Na,K) Alf (2). ‘The reaétion Of these fluoride complexes with silicon dioxide is very slow. It is possible that the silicon tetrafluoride in the solution has to be below a certain level before the aluminum fluoride complex will react with the silicon dioxide. Figure 2 shows a very strong correlation between increasing levels of aluminum in the phosphate rock and increasing levels of fluorine in the 54% phosphoric acid. As expected, an increase in the level of fluorine present in the phosphoric acid results in an increase in the defluorination times. Figure 3 shows the relationship obtained between increasing aluminum in the phosphate rock and the defluorination batch times. These correlations were developed from an intensive study of acid defluorination Parameters at New Wales. SILICA DELIVERY and UNLOADING At New Wales the facilities for receiving silica allow delivery in either pneumatic trucks or railcars. The silica is transferred from the carrier into a storage bin via a filter/receiver located on top of the bin, The filter/teceiver discharges directly into the storage bin. Located below the silica storage bin is a slurry tank. Here an operator mixes a “batch" of silica with fresh water. The % solids of the silica "batch" is monitored. A chart shows the approximate volume of silica slurry to be transferred to the tanks containing the phosphoric acid solution, depending on the $ F in the acid and the % solids in the silica slurry.FLOW SHEET The stripping of the fluorine from the phosphoric acid is accomplished with forced circulation evaporators. This is a “batch” process. Figure 4 shows the flow sheet. Either 40% acid, 54% unclarified acid (ROP) or 54% centrifuged acid (merchant acid) is received from the Phosphoric Acid plant and stored in an agitated tank, referred to as a batch tank, When the acid transfer is complete, the silica slurry is added, and the reactions to form silicon tetrafluoride start. The acid is then pumped to an evaporator where heating and stripping of the fluorine begins. The acid is circulated through the evaporator and returned to the batch tank. This closed loop operation is continued until the P/F ratio for that particular batch is greater than 100. In the evaporator, steam is added to the heat chest, the acid is heated and water vapor is evolved, The fluorine disengages from the acid in a gaseous form, as either silicon tetrafluoride or hydrogen fluoride, Fresh make-up water is added to the evaporator at a rate equal to the quantity of water vapor evolved, The strength of the acid is maintained between 55-57% P205 because the fluorine evolution is faster. when the batch is completed, that is, the ratio of the P/F is greater than 100, the feed to the evaporator is stopped. The acid is then transferred from the batch tank to a defluorinated acid storage tank. Another batch of acid is then received from the Phosphoric Acid plant, and the process is started again. The option exists of dumping the evaporator after each batch or starting a new batch with an evaporator full of defluorinated acid. This is an economic evaluation depending on the size of the evaporator units and the batch tanks involved, because the time required to dump and refill the evaporators also has to be considered.PROCESS DESCRIPTION The key to the operation of the process is the evaporators. The units are Swenson forced circulation evaporators with a barometric condenser and two-stage ejector set with an intercondenser for vacuum control. The defluorination evaporators operate at higher temperatures (200-220°F) than the evaporators in a Phosphoric Acid plant. A double layered rubber consisting of a chlorobutyl layer with a Triflex backing is used to allow for the higher temperatures. The acid feed flow to the evaporators is controlled with a flowmeter, The evaporators are controlled by two of the following three variables, with the third one being a result. They are: (i) temperature (ii) pressure (idi) concentration Normally, the first two parameters are controlled and the concentration is a result, To ensure that the fluorine is evolved with the water vapor, temperatures over 210°F are required. The lower the absolute pressure, the higher the resulting acid concentration will be, which will facilitate fluorine stripping. Acid strength between 55-57% P205 is good for stripping the fluorine. ‘The higher the P205 strength the better the fluorine evolution, but the viscosity of the acid becomes a problem above 58% P205. ANALYSES Samples are taken every two hours, and the fluorine level is analyzed and monitored by the operators inthe plant. 1f the fluorine remains the same for two consecutive samples, prior to the completion of a batch, additional silica is added to the batch tank to improve or restart the reaction. When the level of the fluorine falls below 0.30%, the samples are submitted to the Quality Control Laboratory where the percent P205 and F are determined so that the P/F ratio can be obtained. Samples are then collected and submitted on an hourly basis. Operating policy requires two consecutive samples with a P/F ratio better than 100 (or 175 to meet some states requirements) before the batch is considered complete.DEFLUORINATION PROCESS Figure 5 shows the change in fluorine with time during a Gefluorination cycle. The initial fluorine is lost very rapidly, and the slope of the curve is very steep. It is believed that the steep section of the curve corresponds with the evolution of the silicon tetrafluoride that is readily available in the acid. After that initial loss, the curve then flattens out, and the majority of the time is required to remove the remaining fluorine to obtain the P/F ratio of 100 (or 175). ‘The flat section of the curve probably corresponds with the fluorine present in the acid as fluosilicates and metal fluorides. Three different curves are shown in Figure 5 indicating the possible effect different levels of initial fluorine can have on the batch times. As a general rule the batch time is reduced as the percent fluorine present is reduced. However, this is not always the case, There are numerous factors that will affect the overall defluorination rate and therefore the time, Some of these are: - the form that the fluorine is present in, as discussed in the chemistry = the P205 strength of the acid - the evaporator operating temperature ~ the steam rate to the evaporators = the absolute pressure on the evaporators = the quantity of silica available for reaction ~ the reactivity of the silica Figure 6 shows that the normal trend expected is an increase in the batch times as the % F in the phosphoric acid increases. This data was accumulated at the time the trend with the increasing aluminum in the rock was noted and corresponds with the data shown in Figures 2 and 3. the quantity of the solids present in the phosphoric acid solution is important. A study at New Wales indicated that at least 35% of the fluorine present in the phosphoric acid is in the solids phase. Therefore, when the solids increase, the % F increases. This explains the lower %F present in merchant acid (centrifuged acid) which normally results in lower batch times. Table 1 shows data collected on the changes in the fluorine content for the combined acid solution, and the liquid and solid phases separately during a defluorination cycle. This data is also presented graphically in Figure 7.The fluorine in the liquid phase is reduced very quickly at the beginning of the process. Conversely, the fluorine in the solids is reduced at a slower but steady rate and then it stops. This further supports the chemistry discussed earlier on the detrimental effect of the complex fluoride salts which tie up the fluorine in the solids and take a very long time to react. PILOT PLANT The Development Engineering group at New Wales has a small evaporator that is used for defluorination tests. It is used primarily to evaluate different silica sources. Screening tests are done here rather than in the AFI plant. Figure 8 shows curves from test runs comparing silica samples obtained from different suppliers. The control sample is the present silica source that is being used. As shown, both silica samples 2 and 3 did better than the control, whereas sample 1 was in progress for a much longer time and still had not reached a P/F of 100, so the test was aborted. with this information, economic calculations are made to determine if it is feasible to test the material in the plant, If so, then a plant test will follow with further evaluation. Figure 9 shows another test done with different quantities of stoichiometric silica available for reaction in the phosphoric acid. The control sample had. no silica added, and as noted there was very little change in the initial P/F ratio. At about 60% stoichiometric silica the curves flatten out at P/F=50; at 90% stoichiometric silica the P/F ratio of 100 was achieved. The two different silica sources tested at this time were essentially the same. This data also shows the need for adequate silica to be present for the reactions discussed earlier to occur and reduce the P/F to 100, 90% stoichiometric is a safe quantity to have present, depending of course on the reactivity of the silica. Additional silica is required when defluorinating to higher P/F ratios, At times different parameters have been tested such as the quantity of free sulfate present in the acid and its effect on defluorination. The effect of different types of chemicals that could possibly reduce defluorination times have also been tested in the past. To date none of these tests has shown any significant promise.SUMMARY With phosphorus being an important element in the growth of animals, the value of obtaining feed supplements from such an abundant supply as the phosphate rock is advantageous. The presence of high levels of fluorine in the phosphoric acid, which has a detrimental effect on the animals when received in large quantities, requires an additional step to remove this fluorine before the phosphoric acid can be used in animal feeds. The ability to strip the fluorine using the forced circulation evaporators to produce a defluorinated acid with a minimum P/F ratio of 100 (or 175), has allowed the use of the phosphoric acid in this application, This method is typical of most feed-grade phosphate manufacturers. once the fluorine is removed, the acid is considered to be feed-grade quality. This means that any product added to the process from this point on has to meet the Food & Drug Administration (FDA) approvals for feed-grade quality, Even though further purification would be required for use in human products, the product is regulated by the FDA. The defluorinated acid is then used in a granulation plant to produce various products which will meet the specifications for the P/F ratio greater than 100 (or 175). In addition some is sold to customers requiring a liquid based phosphate for their blending purposes.ql) (2) REFERENCES Becker, P, - "Phosphates and Phosphoric Acid - volume 3” Slack, A. 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