DIAMMONIUM PHOSPHATE QUALITY - 1988 to be presented at american Institute of Chemical Engineers Convention Clearwater, Florida May 1988 by G. M. Lloyd Florida Institute of Phosphate Research and . P. Achorn, Chief Chemical Engineer R. 4. Scheib, Research Chemist Tennessee Valley Authority TENNESSEE VALLEY AUTHORITY Muscle Shoals, AlabamaDTAMMONTUM PHOSPHATE QUALITY - 1988 The following paper is the result of the cooperative study by the Florida Institute of Phosphate Research (FIPR) and the Tennessee Valley Authority (TVA). This project was financed by FIPR. The worldwide production of diammonium phosphate (DAP) is 23 million tons annually. Most of this product is produced using technology that was developed by TVA in the early 1960s (1). In 1986 TVA, PIPR and The Fertilizer Institute (TFI) conducted a seminar concerning DAP quality. Representatives from most of the DAP producers in the United States were present for the meeting. During this meeting the need for good quality DAP products was emphasized, so that we can maintain our dominance for sale of this product in world trade. In 1984 the U.S. phosphate producers supplied 75 percent of the total world trade of DAP. In 1985 this percentage decreased to 73 percent and in 1976 it had decreased further to 61 percent. Some of the reasons for this decrease were the high value for the U.S. dollar and the depressed world market for DAP. A resurgence in, foreign trade occurred in 1987; the U.S. retained approximately 75 percent of the 17 million tons of DAP which was sold in world trade that year. However, some see this as part of a cyclic market for phosphate trading and not a prediction of sales levels for the future. The general trend is that the U.S. is losing its dominance in the marketing of DAP in the world trade. It is expected that competition for the world trade of DAP will increase as other countries increase their capacity to produce DAP. Therefore, it is vitally important that we maintain a high quality granular DAP so that we can retain our portion of the world market for this product. Some have proposed that as theimpurities are increased in our phosphoric acid and phosphate rock, we should decrease our grade. It is the opinion of the authors of this paper that this would be counterproductive to increasing exports of DAP from the U.S. In the FIPR-TVA-TFI DAP Quality Seminar (1986) it was emphasized that we must continue to meet the minimum requirements of the 18-46-0 grade (2). At this same meeting most agreed that the problems in meeting ‘this grade were associated with rock quality, acid quality, and production methods. Widely accepted views are that wet-process phosphoric acid (WPA) chemistry and production methods are the key to making on-grade DAP. Based on these remarks, both FIPR and TVA agreed that a study’ involving correlation of DAP quality and production parameters was justified. FIPR agreed to finance this study. The study has two parts. Part A is the collection of DAP samples and operating data from the, DAP producers in Florida. The samples were analyzed and the operating data were collated. This paper covers most of this data. Part B will be based on data received from Part A and will include bench scale and pilot plant tests. In Part A of the study, 12 DAP samples from representative producers were analyzed and characterized to document the degree of present-day industry's difficulties with impurity compounds and on-grade production. Questionnaires were sent to most of the Florida producers of DAP.operating data were received from 10 companies that answered these questionnaires, We want to thank these companies for readily agreeing to answer the questionnaires. To insure confidentiality we limited the number of personnel who know the names of the companies. When questionnaires were received, each company was designated by a letter and the data were then collated to acquire industry production parameters. only two persons have access to the company letter code. Chemical analyses for the pertinent components were made. Optical, x-ray diffraction, infrared and scanning electron microscope analysis for the compounds in the samples were performed. Process Description Figure 1 shows a flow diagram of the original TVA process. Through the years it hes been changed somewhat by the producers. The process uses a preneutralizer tank, granulator, scrubber, dryer, cooler, and product screens. The phosphoric acid feed is usually split with part going to the scrubbers and part going directly to the preneutralizer. Most producers add filter-grade acid (28 to 32% P20s) to the scrubber and concentrated acid (40 to 58% P20s) is added to the preneutralizer. The preneutralizer is a tank-type that is usually made of 316L stainless steel; however, some preneutralizers are made of mild steel and lined with acid brick.The granulator is a typical TVA-type rotary anmoniator-granulator (3). In operating the plant, partially ammoniated acid from the serubber is fed to the preneutralizer with concentrated acid and anhydrous ammonia. Enough ammonia is added to the slurry to maintain an mole ratio of about 1.4:1 to 1. . Slurry is pumped and sprayed onto the bed of material in the granulator where additional ammonia is added to increase the N:P mole ratio in the product from the granulator to about 1.9. Contrary to the original process, the usual current design is for the product from the granulator to be dried and then screened; therefore, usually hot recycle (crushed oversize and fines from the screens) is recycled to the granulator. Only the product size is cooled and sometimes part of this cooled product is also recirculated to the granulator to control the recycle rate and liquid phase in the granulator. ‘Typical operating data from conventional plants are tabulated below: Scrubber W:P mole ratio 0.5-0.7 Specific gravity 1.3-1.35 Temperature, *F (slurry) 1150-200, Preneutralizer W:P mole ratio L.d-1.$ Specific gravity 1.45-1.55 Temperature, °F 240-250 Slurry moisture, % 25-20 Granulator product N:P mole ratio 1.9-2.0 Temperature, °F 190-215 Moisture, % 34 Dryer, product temperature, °F 170-200 Cooler, product temperature, °F 115-145At the FIPR-TVA-TPI Seminar, it was apparent that no one had the complete answer to what causes the production of low-grade DAP. Most producers admit that making on-grade DAP is becoming more and more difficult. The most frequently mentioned reason was the difficulty in economically disposing of high-phosphate sludge removed from the acid in order to make DAP grade. Correcting this trend by increasing acid clarification leads to less P20: for DAP and increased MAP and granular teiple superphosphate (GTSP) production. The producers that had little or no problem in making on-grade DAP were those using high-quality acid. Lower amounts of Al and Fe and higher amounts of Mg differentiate the Worth Carolina acids from the Florida acids, while the Western acids have lower amounts of Mg and Fe than Florida acids. Thus, producers of DAP who use phosphoric acid produced from Western and North Carolina phosphate rocks have different problems from those who use Florida ores. Plant Operating Data Table I shows the operating data and chemical analyses that were received from the 10 producers of DAP that use Florida phosphate rock for the production of phosphoric acid that is used to produce DAP. ‘The summary of the scrubber operations is as follows:Scrubber operation Averare Inlet acid temperature, °F 130.67 Inlet gas temperature, °F 189.14 Exit gas temperature, °F 155.50 Exit liquor temperature, °F 177.00 Specific gravity of exit liquid 1.39 Mole ratio of exit liquid 0.86 % of acid P20s input to scrubber 33.9 Minimum 100 110 lio 148 2.02 0.4 27.7 Maximum 183 250 180 200 1.55 1.67 40.0 Range 63 140 70 52 0.53 1.27 12.3 The P20s concentration of the acid to the scrubber varied from about 28 percent to 40 percent. Mole ratios in the scrubber varied from 0.4 to 1,67; however, maximum ranges were in these plants that use two-stage scrubbing. Usually the scrubbers were operated at an N:P mole ratio of around .4 to .8. With this mole ratio there should be little or no fluorine loss from the serubber (4). Specific gravity of the slurry from the scrubber was about 1.40. A summary of the preneutralizer (prereactor) operations is tabulated below: Preresctor operation Average % of total ammonia input to prereactor 62.18 % of acid P20s input to reactor 50.63 Inlet acid temperature, *F 136.00 Specific gravity of discharge slurry 1.55 Mole ratio of discharge slurry 1.49 Temperature of discharge slurry, °F 242.3 Slurry retention time 48.36 (Liquid volume (g)/gpm discharge) Minimum 1 1 50 ° 100 52, 245. 210 20 Maximum 72 70 150 1.59 1.58 255 90 Range 22 70 50 0.08 0.13 45 70These data show that average mole ratio of the slurry is about 1.49. The average specific gravity was about 1.55 and the temperature of the slucry that is pumped to the granulator is 241°F. Data from other published and unpublished studies indicate that with these conditions, all of the enmonium phosphate crystals in the slurry should be as DAP and I since the mother liquor of the slurry is ammoniated after it is added to | the granulator, all of the ammonium phosphate crystals that form in the grenulator should be as DAP; the resulting product should contain no monoammonium phosphate (MAP) (5). However, our current data indicates that this may not be entirely correct since some of the samples which we received did contain some MAP crystals. Additional data is required to re-establish these operating parameters to insure that no MAP is within the product. It was anticipated that this is the type data we will receive in the pilot plant tests of Part B of this study. A sunmary of the granulator operating conditions is shown below: Average Minimum Yaximum Range % of total ammonia to granulator 37.82 28 50 22 Recycle ratio (x:1), 3.97 3 5 2 tons recycle/ton product : Granulator retention time, min. 3.72 1.8 5 3.2 Recycle temperature, °F 179.17 165 190 25 Input slurcy temperature, °F 238.50 210 260. 50 Discharged product temperature, *F 200.90 180 215 35 Exit gas temperature, °F 170.00 120 220° 100,These data show that the average recycle rate was about 4 tons of recycle per ton of product with some producers having recycle rates as low as 3 tons of recycle per ton of product. None of the producers actually measured the tons of recycle per hour. It was assumed that the limiting equipment in the plant was operated at its maximum capacity and with this data it was possible to determine the total tons of throughput in the plant. Knowing the production rate, the recycle rate could then be calculated. Data show that the average recycle temperature was about 10°F, which indicates that in all instances the companies used hot recycle. Average temperature of the product from the granulator was about 200°F with a maximum of 206°F and at this temperature, pilot plant physical chemistry data and nitrogen balance calculations indicate that there would an excessive loss of ammonia from the granulator (estimated as high as 25% of total). This anmonia is recovered in the scrubbers. However, there is no convenient way to add awmonia to the product after it leaves the granulator. For this reason, some of the companies added extra sulfuric acid and ammonia to supply supplemental nitrogen as anmonium sulfate while others added urea as a source of supplemental nitrogen. Th future studies we hope to determine ways that we can eliminate the need for this source of supplemental nitrogen without adversely affecting the production rate of the plant. Generally, the companies that had low granulator product discharge temperatures did not require the addition of supplemental nitrogen materials. Perhaps it may be advantageous to cool the recycle and increase the airflow through the granulator. This may~3- cool the product in the granulator and in turn may cause production to increase and ammonia loss from the granulator to decrease. These studies will be included in the next part of our test program. Chemical Analysis: The chemical analyses of the 12 DAP samples are shown in Table 2. These samples were analyzed by TVA's Research and Development Support Laboratory. This analytical laboratory (R&D SPT) was formerly designated as TVA's General Analytical Laboratory. Tabulated below is a summary of analysis of a check sample from this analytical laboratory as compared to the grand average (Grave) of analysis from 30 to 35 other analytical laboratories. Analysis of Interlaboratory Check Samples Sample __ Pa Wo. Type Lab w Total cr ‘avail = _120 0987 DAP «sTVA-R&D SPT 17.86 26.28 0.14 46.25 2.34 Grave 17.86 46.42 0.13 46.21 2.34 The methods used to run are shown in our references for this paper (8) (7). Members of the Association of Florida Phosphate Chemists (AFPC) also participated in this check sample analysis program. Their results-10- are part of the grand average results. The data show the analytical results from TVA's analytical laboratory compare very favorably with the Grave results from the 30-35 analytical laboratori Due to a delay in contract authorization, the samples were received by TVA in 1986 but were not analyzed until 1987. However, the samples were sealed and there was no possibility for contamination by outside sources. : ‘The chemical analyses (Table II) show that one of twelve samples made the actual grade of 18 percent and 46 percent Ps0s. This represents 8.3 percent of 12 samples. In a similar study that was conducted in 1981, 65 percent of the samples had an actual 16-46~0 grade (8). Analysis also show three samples (Sample 8, Plant £; Sample 4, Plant G; and Sample 5, Plant D) would have met specifications if the citrate insolubility had been reduced. Also, all but three of the samples would have met the average grade tolerance for most states’ in the United States. Only three samples would have received penalties from the state control officials. Although this is legally correct, it is not a good sales practice to supply DAP that contains less than 18 percent nitrogen. Tt is especially true when a surplus supply of DAP is available. The analysis also show that seven samples had a nitrogen content of 18 percent or more. Five did not contain supplemental nitrogen either as urea or ammonia and HsS0.. Data show five of the twelve samples met the nitcogen specification without the need for urea, ammonium nitrate or ammonium sulfate being added to them. ‘Two of the four samples that had-1- supplemental nitrogen were deficient in total W content. There was no analytical evidence of nitrate nitrogen being used as a supplemental source of nitrogen in the DAP at the time these products were produced. ‘The calcium levels in the samples ranged from 0.18 to 0.42. These levels were lower than the values found in the 26 samples reported in the 1982 study. Some of these earlier samples had caleium levels higher than 0.42, This reduction of calcium indicates that there has been improvement in the care in which the acids are filtered. The analysis show the Fe levels generally are higher than those found in the 1981 study, Six out of the 12 samples had concentrations greater than 1.2 percent Fe; whereas, in the 1981 study only 5 of 26 samples had Fe contents greater than 1.2 percent. These increased Fe contents are probably due to the ore which we are currently mining. the increased Fe content can cause us some problems with citrate insolubility and Fe compounds have a significant diluting effect on grade. The fluorine values generally were higher for these survey samples —— 8 of the 12 had greater than 2 percent F. The 1981 study showed that 10 of the 26 materials had greater than 2 percent fluorine. The higher fluorine values found in the current DAP study also are in line with recommendations that were made in the 1981 study. Tt is believed that with the higher fluorine contents, there is less possibility for the-12- formation of insoluble P20s compounds in the product as the acid is anmoniated. Also, from the data it is evident that the producers are attempting to reduce the amount of fluorine in the gypsum ponds by utilizing larger amounts of fluorine in the product Optical, X-Ray, Tnfrared Table III is the chemical analyses of water insoluble fractions of the 12 samples of DAP and these observations were used to identify the compounds in the sample. Technique for extraction was as follows: a weighed sample of 50 grams of fertilizer was washed at room tenperature until no crystalline DAP was apparent by polarized light microscopy (PLM) examination. ‘The insoluble residue was then washed with water and then with acetone. Drying was accomplished by pulling air through the material. Table IV lists the observations that were made of these samples using polarized Light microscopy, x-ray diffraction (XRD) and Fourier transformed infrared (FTIR) examination and analyses. Table V contains the calculated amounts of the compounds believed to make up the materials in each DAP sample. These calculations are based on the chemical analysis and the identifications made by PLM, XRD, and FTIR. The water-insoluble fraction contained a small amount of an unidentifiable compound occurring as rod erystals. ‘The optical and other data gathered from the material showed that this unidentified compound was a material that had not been seen before in ammonium phosphates-13- examined at TVA. Scanning electron microscope/enersy-dispersive X-ray analysis of crystals of the material showed that it contained large amounts of phosphorous and lesser amounts of Mg, Al, and Fe. Many of the XRD reflections that were unassignable probably are associated with this compound. ‘There were pseudomorphs of FeWH.(HPO«)2 after crystals of FesKiis(P0s)e+4Ha0 present in many of the water-insoluble fractions. The Feskii«(PO«)e-4H20 is present in the wet-process acid from which the DAP is produced, and the presence of its pseudomorph is indicative of the imereased amount of sludge in the current acids. Calculated Percentage of Compounds in DAP Differences in the “Summation values (shown in Table V) compared to the chemical analysis values can be attributed to summation of minor errors in assigned chemical compound composition, estimated quantities of the solids by PLM and ETIR, and chemical analyses. The calculated percentages are the best fit to the chemical data and physical characterization obsecvations. These relatively minor differences appear to validate the selection of these compounds as representing the composition of the DAP and the water-insoluble fraction. The presence of (Mis)sP0« in many of the DAP samples is speculative since there was no direct observation of this compound by any of the-1a characterization techniques. However, this is the most “convenient” means of accounting for the N and P based on chemical analysis and the compounds actually observed. The validity of “excess” ammonia is the most important factor to be considered, and the presence of excess ammonia is evident from ammonia vapors over stockpiled DAP. These data show that samples contained between 64 and 74 percent DAP. Four samples contained a significant amount of MAP which is one of the causes for low N content in the product. The ammonium sulfate content varied from a low of 4.8 to a high of 9.0 percent. Although ammonium sulfate does help to insure the nitrogen content is high enough to’ meet grade requirements, it does have some diluting effect on the P20s of the product. Another compound which the samples contained a significant amount of was iron ammonium phosphate, FeWH«(HPOs)2, which varied from a low of 4.71 to a high of 7.85 percent. This material also has a diluting effect and it has an adverse effect on the N content of the product because its W:P mole ratio is only 0.5 as compared to the desired 2.0. Another significant compound was one that contained Mg, Al, M, P, H, and F with a formla of MgAl(WHa),H(PO4),F2. Tks content varied from a low of 2.9 to a high of 5.2. The compound has a diluting effect and its MiP mole ratio is 1.0 instead of the desired 2.0. All other compounds were less than these three major sources of impurities.~15- It is obvious that most of the problem with grade quality could be eliminated by additional clarification of the phosphoric acid used in manufacture. The dilemma is what to do with the sludge from clairification. Some have used it to make MAP of low grade, others continue to use mich of it to produce triple superphosphate. It is a problem that will probably become more severe as we mine other rock in Florida. Future Studies In future studies we will have the following goals: 1, Increase production rate. 2, Improve grade control and quality (dust, hardness, etc.). 3. Determine the maximum amounts of impurities (sludge) that can be added without reducing grade. 4, Discover impurities which may be conveniently removed. 5. Determine recommended operating procedures and equipment designs by which the formation of citrate insoluble P20s compounds can be avoided. 6. Combine impurities (ca, Mg, Fe, Al, F, K, ete.) with ammonia in high N:P20s ratios. 7. Reduce losses.~16- We will be using the data presented in this paper and data from bench-scale and pilot plant tests to formulate recommendations for our DAP industry to use in attempting to reach these goals. We have submitted a proposal to FIPR for this project.References Achorn, F. P., et al. “Process for Production of Diammonium Phosphate," U.S. Patent No. 3,153, 574, Tennessee Valley Authority, Muscle Shoals, Alabama, October 20, 1964. DAP Quality Seminar by Florida Institute of Phosphate Research-Tennessee Valley Authority-The Fertilizer Institute Florida Institute of Phosphate Research publication No. 01-000-041, Bartow, Florida, March 1986. Mielson, F. T., et al. “Apparatus for Awmoniation of Superphosphate,” U.S, Patent No. 2,741,545, Tennessee Valley Authority, Muscle Shoals, Alabama, April 10, 1956. Bont, J. “Fluorine Emission Control New UKF-NPK Plent at Pernis, The Netherlands," ISMA Technical Conference, November 1980. Young, R.D., G. C. Hicks, and ¢. H. Davis. “TVA Process for Production of Granular Diammonium Phosphate,” Agricultural and Food Chemistry, Vol. 10, November/December 1962, pp 442-447. (TVA Reprint. op-317). Total P20s (1st run) ~ AOAC Mo. 2.029-2.031, Alkalimetric Quinolimium Molybdophosphate Method; (check analysis, 4 samples) - AOAC No. 2.021-2.025, Spectophotometric Molybdovanadophosphate Method. CE P20s - AOAC No. 2.046(b), Spactrophotometric Molybdovanado- phosphate Method. Dillard, E.F., et al, “Precipitated Impurities in 18-46-0 Fertilizer Produced from Wet-Process Phosphoric Acid,” TVA Bulletin No. ¥-162, 1981.nan O98 U8 eSUgetetrite ee sonetnona traWEtrireerricerri reed) a | a3 7 Z, TCE eee | | ‘ tees aa ae Sausahuengeggngnss42 cocccccccccccccsceceen ors reteda soqeroenst Sasa cecal ¥ 7 7 ¥ o s © sntono SB ES HONEY TAL VATTAALE WOOT HTH" Y6 WTTETTSS2 oSeasenggge.coer eee were c r T ¥ s 7 ¥ 7 os funteegvecemstetor Ra/pognitt 8838888 anaes 3 dasses3(08H puE “ PoT;TIWepyUN UE poufequos oTdues styLy *SySATRUE TeDTuIOYS woss PazPTNOTeDD “AULe9 Fado potzTqUepry *kdoosoaqoeds posnazuy wrossuesy soyanog fq p9t3 1 Ueptg ‘syskqeue Avs-x Aq poy;tquepre WO FTO TO S¥D 980 TTT. 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(rHiN) 00°0 00°90 0079-000 00"0- 0070-000 0070-00-00 LE*O BLO pe (HNO 00°90 £19 0079-000 -——00"0-— 0070-000 00"9-—0070—zS0 00-0 GB“ prodzHen 80°0 00°90 -00"0 0" 0020000070090 S70. 0a“ rodent 00°0 —00°0 = -00"9 "0 00"0 000-0" GO" 00°00 0S“ 9 pPOSE (PHN) 90°0 000 000-000-000 00"9-—oT0-—-0070-—«0070- 000-000 —OT"0 prors 00°90 000-0000" ODD 00] zL70D'D-SsE"E SsEOT'Z peatse (PHN) 00°0 000 00°" 000 00"9 "0.0070 wD'0sODszSz ge" qF (°0dH) PHNeS, 00°0 = 00°0-_z¥"0 000 0"0- "D009 =O] «OND GFT = «ZOO pF (POdH)? (rH) eD, 00°90 00°90 +900 009 += -9Z"9_~— 009-000-0070 00-0079 ETOszez gq (70aH) FHNTY 00°0 00°90 000-000 ¥EO_-—0070 00700070 wBO LTO ER'Z qt ezarOdtHiNty 00°90 —00°B 009TH wZ"O 009-009-0090 "0S —sEO'T otqted1V-8H 90°90 009 009 = @Z"O_—-$Z"O_— 0000000 SEO BET 920 RZ gtetae(POAIHEC HN) IVR 9S eTdues *5 OT a 201s, FOS, a 50d a tw punsdioy ¥ ave Uy Spann: FO OIPFUTTIST PSTeTTESinued) ( TABLE V, Calculated Percentage -AL Me Ca Fe ‘Sioa ‘S00 Fads ut & Compound Sample 6 0.00 0,00 0.06 0.00 0.00 0,00 0.00 0.00 0. 0.00 0.00 0,00 0.00 0.26 0.00 0.00 0.00 0.00 0.00 0.00 0.34 0.10 0.00 0.00 0,00 0.00 0.00 0.00 0.00 0.00 0.00 0.38 0.22 0,27 0.04 0.00 0.00 0.00 0,00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.45 0.00 0,00 0.00 0.00 0.00 age ocd 338 ocd 0.54 0.60 0.38 0.00 0.00 0.00 0.59 0.00 0.00 0.00 0.00 2.01 0.00 0.71 0.00 0.92 3.69 0.00 0.00 0.00 0.16 0.34 37.04 0.40 0.00 0.14 0,02 0.18 0.36 0.14 0.00 1.51 0.00 0.00 14.60 0.44 4.a7 0.91, 1.80 0.38 1.86 6.90 0.92 0.22 7.13 0.31 0.57 68.85 MgAl (MHts) aH(PO4) 2F2> Mg-Al-¥asb, ALMiLAHPO«F 2352 ALWHs (HPO4) 2? 0.00 0.00 0.00 0,00 0.00 0.00 0.09 0.00 0.00 0.00 0.00 0.31 0.22 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0,00 5.18 0.00 0.00 Ca(Nile)2(HPOs)24 Feuitts (HPO4) 25 Clits) a3ived sioad 0.00 0.00 0.00 0.00 0.11 (Allts) 28048 +e Kil2P04d MaliP04d (itis) 2HPO«a +e (ita) sPO0d Total H208 0.74 1.54 3.46 45.60 2.11 5.18 0.53 1.48 0.91 0.480.260.1009 17.80 99.33 Summation 45.60 2.12 5.18 0.53 1.45 0,910.48 0.26 0.11 0,09 17.80 Chemical analysis @ydentified by x-ray analysis. Digentified by Fourier transform infrared spectroscopy. Identified optically. calculated from chemical analysis.‘sysAjeue Teoqwoys wosy pazetnaqeg, “ArTeOT3d0 poy at qUuePLy *Adovsoaqo0ds paseazuy wiojsuesy Jopanog hq poTITIWEPIg ssyskteue kea-x fq_poqayavepry 6070 OL0 90 HHO SLO SHUT GTO LY BLT oR'SY Ore syskqeue [eoqueyo 60°0 OT70 «9770 WTO GBD SHE «GT's 9L*¥ BLT OB'SH OUST 986 wor qewuns, 962 porn TeI03, SUSE OTTWT Lv'99 ateYOdH? (PHN) i a prodeHrHN 90°09 00°90 00°0 009-009-000 00"0- 000-000-000 060 GT pe (ZHAO 00:0 0T"0 000-0" 00"0-00"0 «009-09 0D——stETO OTD zS70 prodzHeEn 60°09 00°0 00°0 000-000-000 009-079" MTD ODEO prodtHx 90°0 00°09 000-000-000 00"0— 000% =~ 000 GET SSS terose (HN) 00°0 00°90 -00"0 0" 00 00"0 «T0909 000 00700900 prors 00°0 009» «90"0- "9 00°0-00"9-SGT'0.. "0 =~ SEO." GOTDSSS"0 pedis? (rHN) 00°90 00°0 00°0 000-000 S¥'T 00°00" «0070 NE BED O89 2tqe(OaH) rHNad 00°90 00°09" 000-0070 00"-—S 097000790070 -z60 TORT pe(PORH)E (PHN) ED, 0070 000-0090" kZ*O 000-0000" ETOH zB" qte2a?OdHrHNTY 90°09 00° 00"0 800 LTO 00000000 L¥TO «00D DOT" atqted-1V-3h 00°0 = 00°0 000 9EO OVD O00 CD] 0] ESO LZ POSEY gt eat C>OAIHE (PHN) TR ¢ etémes x hr zd a W wa OS OS Tord a pURSaIOS ¥ WT UT spunddOD Jo SsaIuSSIET poeTNOTED PENT AWOD| aveGalculated Percentage of Compounds in DAP w P20s FE 30s, Sid Fe a Me a Wa, we % Compound Sample 8 0.00 0.00 0.00 0.00 0.00 0.39 0.12 0.43, 0.27 0.13 0,12 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0,99 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0. 0.00 0.00 0.60 0.77 0.18 0,00 0.00 0.00 0.71, 0.00 2.26 0.00 0.34 0,00 0.67 2.52 0.00 0.00 0.00 0.07 0.31 39.57 0.45 0.00 0.07 0.06 0.13 0.25, 0.18 0.00 1.01 0.00 0.00 15.60 02 5. ‘MgAl (Ha) aH(PO) aF22+P Mg-AL-F)B,e 1 0.85 1.04 1.36 an wn 0.22 ALNHaHPOaF 2> 0.00 0.00 0.00 0,00 0.00 0.00 ALNII4 (P04) 2 Ca(NHa) 2(HPO«) 24 Fela (11P04) 2 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 (Ha) 2SiF6 sioa? 0.00 0.00 0.00 0.04 0.00 0.38 0.22 0.00 0.00 (alla) 280436 KitaP0«4 WaHtaPo.t 0.52 73.56 (ata) at1P048€ (iltia) P0484 ‘Total Ha0d 0.77 0.46 46.50 2.27 «3.48 «0.60 0.99 0,95 0,510.19 0.10 0.08 18.20 98.88 ‘Summation 46.50 2.27 3.48 0.60 «0.990.950.5119 0.10 0.08 18.20 Chemical analysis Bygentified by x-ray analysis. bidentified by Fourier transform infrared spectroscopy. Craentified optically. 4caiculated from chemical analysis.a TABLE V_ (Cont: Calculated Percentage of C ca HE Sioa Fa AL ‘S08 20! we % Compound Sample 9 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.09, 0.00 0.00 0.00 0.00 0.00 0.00 0.57 0.58 0.17 0.00 0.00 2.15 0.00 0.42 0.00 0.06 0.24 0.35 4.79 0.87 0.78 2.43 6.66 1.08 bye MigAL (WH) 2H(PO4) 22840 AlNHaHPOar 22> Mg-A1-F+ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.17 0.00 0.00 0.34 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.31, 1.20 3.56 Ca(IHa) 2(HPOs ) 24 FeNHa(HPOs) 2> (ita) 28iF6! sioat 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.40 0,00 0.00 0.00 0.00 0.00 0.35 0.00 0.00 0.31 0.00 0.00 0.00 0.00 A.79 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.16 0.52 0.00 1.89 36.60 1.40 0.00 0.00 0.06 0.37 14.43 6.59 0.31 (Ha) 28048+€ KHaPO«d 0.00 0.00 0.00 0.00 0.89 0.13 3.06 68.04 MaltaP0.? coca) 24 MiatiaPO«d (iia) aHPO4a +e Total 204 2.60 17.50 46.40 1.98 4.79 0.66 «1.40 0.730.460.3417 0.09 98.50 Summation 46.40 1.98 4:79 0.66 1.400.700.4638 0.17 0.09 17.50 Chemical analysis Sydentified by X-ray analysis. Didentified by Fourier transform infrared spectroscopy. Identified optically. Scaleulated from chemical analysis.0.00 0.00 0.00 0.00 0.00 0.00 0.00 wa 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ca 0.00 0.00 0.00 0.00 0.21 0.00 0.00 He 0.28 0.03 0.00 0.00 0.00 0.00 0.00 0.31 0.07 0.29 0.24 0.00 0,00 0.00 AL Fe 0.00 0.00 0.00 0.00 0.00 1.39 0.00 0.00 0,00 0.00 S102 0.00 0.00 0.00 0.00 0.00 0.00 0.15 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.53 0.00 0.00 ‘300 Sample 10 TABLE V (Guatis 0.43 0.20 0.41 0.00 0.00 0.00 0.28 0.00 0.00 0.00 P2038 2.62 0.00 0.76 0.00 0.74 3.53 0.00 0.00 0.16 0.35, 0.07 1.91 0.00 0.00 0.49 14.35 0.32 0.00 0.15 0.13 0.15, wt % 3.62 0.30 1.91 2.13 1.50 6.62 0.44 8.98 0.31 Compound MgAl (NHa) 2H(PO4) 2F2P Me-AL-Fa,D,e Ca( Wis) 2(HPOs) 24 Felis (HPO.) 2? ita) asired (iilta) 2808 ALNH4HPO«F 2450 KH2PO«4 ALNI4 (HPs) 2> 36.38 2 67.64 8 oe NaiaPo4.? WHattaPoad 0.09 0.09 0.07 0.07 0.21 0.21 0.31 0.31 0.91, 0.91 1.39 1.39 0.15 0.06 6.53 6.53 45.90 1.32 45.90 1.32 oscopy. 17.90 17,90 2.92 100.74 bidentified by Fourier transform infrared specter (iia) 2HPO4 +e chemical analysis Sydentified by X-ray analysis. erdentified optically. dcalculated from chemical analysis. Total H20¢ Sunmation‘syekwus TwoTwoyD wos; poreTN>TeDD “Atteotado poystwepry *Adossoayzeds paseajuy w20suesy r9yInog ka pOTITIWOPTg *syskteus £ea-x hq poyzyqwople z10 ETO Tee GET TT 18 ey BZ oOLSYoesat sysheue TRoTwayD zo ETO TED EO OTT ETE TBO Evy BZ oOL'SH ozBT —T9"O0T voy yewuns serz pOrH TeI0E SOL ST'T 60°F prode cont) Toe 9E°¥E OL"L9 bt ePOdHE (itt) 90°0 —£t"0—00"9-—00"9-—-00"0 00" 009-09 = D0-—zS0— «00D prodzHen ZU'0 00°09 00°09 00"0 00" "0-000 "0S zz70— ze“ prode Hx 00°0 00°09 00"9 000-0" 000000 EH © 000 -ODswz"TCOTD oterOSe Crt) 90°0 00°09 00°9 0070-00" 000 EZ"0~— 009 = «00-00 sEZO prors 00°0 000 009-000-000 009 BS70 000s OTT D9 tzO EL" poatse Conn) 00°90 000 00°90" ODD ETT =~ 00°0 000s ewz wee’ q® (roan) nnea 00°0 00°0—-TE"0_— 000-000-0000" wD VDSsOT'T ae teez pe (POH) = (7HN)eD 00°0 00°09 009-000 O"9—00"0 «009-009-000 qt (*OaH) HNTY 00°0 —00°9-—00"9- 0070 0S"0— 00000] pO"DsstkS zt. qteta?0aNrHINTY 00°09 600 00°8 = TT"0—¥Z"0— 000-0070 00°0 430.000 g00 zo" otqted-1v-8a 00"0 09°90 000-2zz"0 Sz" 000-000 wD SE-OOET =z 'z qPa® (90a) HE CHHN) TV3HH TT etdues ae iT Ww 3a FOS FOS a Foed a ia PurodTES ¥ “SP ear TST aT ET YT SE PRENTWERTUNNE eeRr rT errerIETeIT a eT RITE TREE ERLE nT Rn OT EIN EUT DENTE TN et TPOHUFITCSY A TAT0 0 0.12 sss ood 0.00 0.00 0.00 0.00 88 S656 Ha 00 00 0.00 0.00 0.00 0.0 338 és 0 01 0.00 0.00 0.32 0.00 is 0.27 0.14 0.00 0.00 0.00 0.00 0,00 0.00 0,00 0.00 0.00 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 00 +00 00 0.00 0.00 1.25 0.00 0.00 0.00 0.00 sida _Fe 0,00 0.00 0.00 0.61 0.22 0.00 0.00 0.00 83a oe ‘S04 0.00 0.00 0.00 4.3: 0.00 0.00 Sample 12 1.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 i 0.00 1.13 3.18 0.00 0.00 0.00 0.22 0.59 34.64 0.04 0.22 0.31 0.29 0.00 1.26 0.00 0.00 13.66 a 3 53 0.75, 2.28 5.95. 2.81 0.22 5.93 0,42 0.99 64.39 , d | Z | 3 Gi MgA1 (Ma) 2H(PO«) aF22+b Mg-AL-£2sD,6 Ca(Wita) 2(HPOs) 24 Petia (HPO«) 2? ila) 28iF6 ALHaHPO«F24s> Sioad ALMHa (HPO4) 2D 3 5 2s 38 23 23 0.00 0.12 0.12 0.00 0.19 0.19 0.19 0.00 0.00 0.32 0.32 0.42, onan. 1.08 1.08 0.00 1,25, 1.25, 0.83 0.83 4.31 4,31 3,01 3.01 2.90 45.20 45.20 17 18.00 18.00 99.37 brdentified by Fourier transform infrared spectroscopy. Tfaenti€ied by x-ray analysis. CIdentified optically. ¢ 3 . . a a 38 23 33 ze dcalculated from chemical analysis. Chemical analysis ‘SummationGLVHdSOHd WOINOWAVIC YO WAINONANVONOW YVINNVaD 40 NOILOINGOUd YOd SSAIOUd VAL 40 LAAHS MOTI T ganda GTIAIaa SANIT HLVHASOHd aaAua ' ANINOAAVIC AOLVIONVYD avianvas AOLVINORAY DNINIVINOD |LSQVHXE UaZIIVaLNANadd a ugganuos OdVA WaLVA YOdVA SALVA (0 “rs OL %0e) 07H aiov o1doHdSoHd