Abstract:
Ammonium polyphosphate is manufactured on a continuous basis by reacting gaseous ammonia and aqueous phosphoric acid at elevated temperatures in a one or multiple stage falling film reaction zone in the presence of a diluting gas if desired, using wet phosphoric acid, preferably containing 28-32%, by weight P 2  O 5  and an excess of ammonia. The phosphoric acid and the gaseous ammonia are preferably carried in counterflow and the temperature in the falling film reaction zone is adjusted using heat transfer fluids to within the range of 120° - 260° C.

Description:
This is a continuation of application Ser. No. 429,311, filed Dec. 28, 1973, now abandoned. 
    
    
     BACKGROUND 
     The invention relates to a process for the manufacture of ammonium polyphosphate from gaseous ammonia and aqueous phosphoric acid, preferably in the unpurified state and with a concentration of the order of 28% P 2  O 5 , through the use of a multiple-stage falling film reactor whose individual stages are kept by means of suitable heating fluids at temperatures adapted to the desired degree of condensation, the preheated ammonia flowing against the phosphoric acid descending in a film within the fall tubes. 
     Between the individual stages the vaporous water being released by the concentration and by chemical reaction can be separated by intermediate condensation, while the gaseous ammonia (together with a diluting gas in some cases) is fed to the next stage of the falling film reactor after reheating to the particular reaction temperature. The liquids, generally containing ammonium fluoride, which finally emerge from the reactor, are precipitated in an injection condenser. 
     Ammonium polyphosphate has been gaining in importance as a fertilizer (in solid or dissolved form) and as an additive to detergents, or for use as a flameproofing agent and for other purposes. 
     The manufacture of this product starts out either from superphosphoric acid and ammonia, or from highly concentrated phosphoric acid containing at least 50 wt-% P 2  O 5  and ammonia. In other processes, ammonium phosphate is concentrated by evaporation in the presence of urea. It is also possible to burn phosphorus in the presence of ammonia or to melt ammonium phosphate together with P 2  O 5 . 
     Dilute phosphoric acid solutions or dilute ammonium phosphate solutions are generally first concentrated by more or less tedious processes, usually multi-step processes, before they are delivered to the apparatus in which the actual manufacture of the polyphosphate is to take place. On account of the great amount of corrosive effects which are usually produced during these processes, they are performed at the lowest possible temperatures and therefore usually at reduced pressure. 
     SUMMARY 
     It has now been found that ammonium polyphosphate may be produced continuously without substantial corrosion in a single apparatus and without the use of a vacuum by performing the reaction in a single or multiple stage falling film reaction zone, in the presence of a diluting gas if desired, using wet phosphoric acid, preferably containing 28 to 32 wt-% P 2  O 5 , and an excess of ammonia. 
    
    
     DESCRIPTION OF THE DRAWINGS 
     The accompanying drawing is a diagrammatic view in vertical elevation showing a falling film reaction column that can be utilized in carrying out the process of the invention. 
    
    
     DESCRIPTION 
     For the polycondensation of phosphorus pentoxide in aqueous phosphoric acid solutions or phosphate solutions to form superphosphoric acid or polyphosphates, it is necessary to put in heat, e.g., by heating to temperatures above 100° C. Steam has generally been used for this purpose hitherto, i.e., the exchanger tubes involved must be able to withstand the corresponding pressure. 
     This requirement is unnecessary when appropriate fluid media are used in accordance with the invention. The heat transfer liquids may be high-boiling, aromatic or non-aromatic, inert hydrocarbons, such as silicon oils or other commercial thermal oils. 
     In the process of the invention, the neutralization of the phosphoric acid by gaseous ammonia is simultaneously accompanied by a concentration of the salt solution that forms, plus the polycondensation of the phosphate that is present to polyphosphate. The polycondensation which generally occurs only upon the addition of heat superimposes itself upon the neutralization and wholly or partially consumes the neutralization heat that is released, so that particularly good use is made of the latter in the closed system. 
     The falling film reactor used in accordance with the invention consists of one or more stages or having in some cases separate circuits for the thermal oil used as the heat transfer medium. By establishing different temperatures in the individual stages or zones of the falling film reaction zone, it is possible to favor concentration by the evaporation of water or at higher temperatures, to favor condensation to polyacids. 
     In general, the heat transfer oil is to be introduced into the individual stages of the falling film reactor at temperatures between 120° and 260° C. 
     Through various temperatures of the heat transfer oils in the individual stages and especially through the selection of the temperatures involved, the condensation ratio of the final product may be controlled to a great extent. In general, the lowermost stage will be operated at the highest temperature that is used. 
     In most cases, operation at normal pressure is to be preferred to a procedure at a pressure above or below normal in the application of the process of the invention. 
     Suitable reactors forming falling film reaction zones are described, for example, by H. Brauer, VDI-Forschungsheft No. 457, and H. Smegal and H. Liebing, &#34;Dimensionierung von Fallfilmverdampfern&#34; in Seife, Ole, Fette, Wachse 97 (1971) No. 20, 703-08. 
     It is desirable not to transport the water vapor released by evaporation, neutralization and polycondensation through the entire falling film reaction zone, but to remove it, even prior thereto in some cases. For this purpose circuits are to be provided in the gas phase between the individual stages, in which the water will be largely separated by known methods. Before the reaction gas thus freed of water vapor is returned to the column, it is to be heated again to the working temperature. The heating is performed advantageously in a heat exchanger using heat transfer oil from one stage of the falling film reaction zone for the transfer of the heat. 
     Since the heat of neutralization is entirely utilized in the system for the polycondensation of P 2  O 5 , it is generally necessary during the operation of the falling film reactor only to reheat the heat transfer oil circuits slightly. This reheating, as well as the heating performed at the start, is performed by known methods, preferably in heat exchangers, using flue gases for example. 
     The ammonia that is to be used (as well as the diluting gas, if any) is heated prior to entry into the reaction tubes, generally to temperatures between 150° and 250° C. This heating is likewise performed by heat exchangers fed with heat transfer oil. 
     The gaseous ammonia flows through the falling film tubes, in which phosphoric acid trickles downward along the tube walls, enabling the ammonia to react with the acid. 
     So much ammonia is always put in that an excess exists over the intended molar ratio of P 2  O 5  to NH 3 . In the case of raw acids having very high contents of acid secondary constituents, an even greater excess of NH 3  over P 2  O 5  will be used. Following this practice leaves sufficient amounts of NH 3  in the gas phase to assure the removal of the volatile impurities in the phosphoric acid being used. 
     The vapors emerging at the head of the falling film reactor contain, in addition to the diluting gas, varying amounts of ammonia, ammonium fluoride, fluorine compounds, water vapor and other compounds. This gas mixture must be freed of the fluorine compounds in an intensive separator. An injection condenser, into which dilute soda lye is injected, has proven particularly valuable for this purpose. The ammonia that is thus released is reprecipitated in an acid post-separator. The residual vapors are virtually free of fluorine compounds and ammonia and may be emitted without polluting the atmosphere. 
     The crude phosphoric acid is fed into the top of the falling film reactor and flows down the tubes and through separators from one stage to the next, while they are neutralized and transformed to ammonium phosphate and ammonium polyphosphate. 
     In general, a virtually water-free molten mass will be obtained in the lowermost stage, and will finally drip into the sump of the falling film reactor and may be taken continually or in batches from then for further processing. 
     Depending on the ratio of NH 3  :P 2  O 5 , and depending on the degree of condensation achieved, condensation products of varying composition will be obtained. Thus, in the case of the simplest polyphosphate, pyrophosphate, mixtures between the adjacent compounds (NH 4 ) 4  P 2  O 7  and NH 4  H 3  P 2  O 7  are possible (solutions containing smaller amounts of free acid or even solutions containing free NH 3  are, of course, also producible). In the compounds mentioned, the NH 3  :P 2  O 5  molar ratio is between 4:1 and 1:1, while in the three orthophosphates it varies between 6:1 and 2:1. As the degree of condensation increases the maximum number of NH 3  moles that can be introduced per mole of P 2  O 5  diminishes; thus in the case of (NH 4 ) 5  P 3  O 10  it amounts to 3.33, in the case of (NH 4 ) 6  P 4  O 13  it is 3.0, and in the case of (NH 4 ) 10  P 8  O 25  it is only 2.5. 
     In all these cases, however, acid salts are also possible, so that the NH 3  :P 2  O 5  molar ratio may be between 0 and the maximum figures given. For the manufacture of a pure ammonium salt of polyphosphoric acids, at least 0.5 mole of NH 3  will be used in practice per mole of P 2  O 5 , but for the manufacture of solutions of mixed polyphosphate solutions, fewer moles of NH 3  will occasionally be used per mole of P 2  O 5 . 
     As the experiments performed with apparatus made in accordance with the invention have shown, it is possible by varying the temperature in the individual stages, by varying the acid and ammonia inputs and by controlling the NH 3  :P 2  O 5  ratio, to vary the composition of the products within the range discussed above, preferably between 4.5 and 0.5. 
     In general, the dimensions of the apparatus will be optimally adapted to the raw acid to which preference is given. In the case of apparatus already on hand, however, a broad choice is still available in the composition of the products, as the above-mentioned experiments have shown. 
     Products corresponding to the regular commercial ammonium polyphosphates containing 12 to 16 wt-% NH 4  -N and 54 to 70 wt-% P 2  O 5  (corresponding to an NH 3  :P 2  O 5  molar ratio of 1.75 to 3.00) may be made with reactors constructed in accordance with the invention, generally without difficulty. Preferably, the conditions of production are established so that products containing 14 ± 2 wt-% N and 60 ± 3 wt-% P 2  O 5  (corresponding to an NH 3  :P 2  O 5  molar ratio of 2.4 to 2.84) will be formed. In a product of this kind a pH can be determined (after dilution to a solution of 10% by weight) of 4.3 to 5.2. In other compositions pH values between 2.5 and 6 have been observed. The content of polyphosphoric acid in the total phosphoric acid was, in the products produced, between 25 and 85%. 
     Furthermore, it is possible to add also to the phosphoric acid solutions of compounds which promote polycondensation, such as urea for example. 
     The phosphoric acid to be used may be in virtually any concentration. In raw acids a P 2  O 5  content of 28 to 30% is preferred. If more concentrated or more diluted solutions are used, the conditions of the process are to be adapted accordingly. 
     The amount and nature of the (commonly occurring) impurities in the phosphoric acid present no difficulty in the process of the invention. One need only see to it that an excess of NH 3  above the acid volatile secondary constituents of the raw acid is maintained. Since the virtually corrosion-free removal of such compounds is one of the advantages of the process of the invention, it will be used preferentially for impure raw acids, e.g., for phosphoric acids from raw phosphates having a high fluorine content, or for those which are obtained by treatment with HCl. 
     Acid-resistant steel has generally proven to be a practical material for the falling film reactor, the section condensers and the heat exchangers. For critical parts of the apparatus materials are recommended which are resistant also to fluorine compounds. 
     The gaseous ammonia may be fed into the column either alone or together with a &#34;carrier gas.&#34; All inert gases are usable as diluting gases, e.g., air or nitrogen. Particularly when acids containing more than 40 wt-% P 2  O 5  are used it is recommended that the process be performed with the use of an inert gas. If a diluting gas is used, explosive mixtures with ammonia are of course to be avoided, i.e., in the case of air, for example, mixtures containing more than 13% ammonia by volume. 
     EXAMPLES 
     The acid used in the examples had the following composition: 
     
         ______________________________________P.sub.2 O.sub.5   28 - 30%, by weightF                 1.5 - 2.0% by weightCaO               0.2 - 0.4% by weightSO.sub.3          2.0 - 3.0% by weightAl.sub.2 O.sub.3 /Fe.sub.2 O.sub.3             0.2 - 0.4% by weight______________________________________ 
    
     The amount of solids in the raw acid usually amounted to from 3 to 5 g/l. These were mainly: 
     
         ______________________________________CaO               16%F                 21%SO.sub.3          24%SiO.sub.2         35%______________________________________ 
    
     In the experiments, a two-stage falling film reactor of glass was used with an inside diameter of 4 cm and an effective length of 0.8 m in each stage. Ammonia was used without diluting gas. 
     EXAMPLE 1 
     
         ______________________________________Temperatures:       Stage I, top   ° C                               190 - 200       Stage II, bottom                      ° C                               235 - 240       Product temp.  ° C                               220Charging:   Wet acid       kg/h     4.08       Ammonia        kg/h     0.76Molar ratio NH.sub.3 : P.sub.2 O.sub.5                       5.4Analysis of discharged product: 14.3% NH.sub.3 -N, 54.5% totalP.sub.2 O.sub.5, of which 38.9% was polyphosphoric acid.______________________________________ 
    
     EXAMPLES 2 AND 3 
     
         ______________________________________Temperatures:     Stage I, top ° C                          190 - 200     Stage II, bottom                  ° C                          240 - 250Charging: Wet acid     kg/h    1.9    2.72     Ammonia      kg/h    0.26   0.37Molar ratio NH.sub.3 : P.sub.2 O.sub.5              ˜3.95                      ˜3.95The following values meantime established themselves:     Product temper-     ature in ° C                  220     230-240     Product pH   4.5-4.6 4.5-4.6Composition:     NH.sub.3 -N  wt-%    About 14                                 About 14     Total P.sub.2 O.sub.5                  wt-%    About 57                                 About 57of which  Polyphosphoric                  %       75     70     acid______________________________________ 
    
     With a larger charge per time in the falling film reactor under otherwise the same conditions the product temperature, as shown by Examples 2 and 3, rises from 220° C to 230°-240° C. The composition and the pH values of the reaction products, however, remain virtually unchanged, but the degree of condensation diminishes (due to the shorter reaction time) in the case of the larger charge, from 75 to 70%, for example. 
     Whereas according to these two examples the increasing input to the apparatus only reduces the degree of condensation when the NH 3  :P 2  O 5  ratio remains constant, a variation of this ratio will produce great changes. Thus, according to further examples, when the feeding rate was 0.76 kg of ammonia per hour and 2.17 to 2.44 kg of wet acid per hour (corresponding to an NH 3  :P 2  O 5  molar ratio of 9.6) pH values of approximately 5 were obtained. On the other hand, at 0.76 kg of ammonia per hour and 2.76 to 2.99 kg [of wet acid] per hour (corresponding to a molar ratio of 7.7), pH values of 3 were obtained. 
     No disturbances were caused in the experimental runs by solid impurities.