Patent Publication Number: US-2021179458-A1

Title: Method and assembly for recovering magnesium ammonium phosphate

Description:
The invention relates to a method for recovering magnesium ammonium phosphate (MAP) from sludge supplied to a first reaction tank in which an aerobic environment prevails and in which the sludge is guided in a cycle supported by aeration, with cationic magnesium such as magnesium chloride being added to the sludge and magnesium ammonium phosphate crystals (MAP crystals) precipitated from the sludge being removed via an extraction device provided in the floor area of the first reaction tank. 
     The invention furthermore relates to an arrangement for recovering magnesium ammonium phosphate in sludge treatment, comprising a first reaction tank with a cylindrical upper section having an inner area and an outer area and merging into a lower section having a conical shape, from which section extends in turn an extraction device for magnesium ammonium phosphate crystals, at least one aerator device being provided in the inner area of the upper section of the first reaction tank. 
     Phosphorus is a vital substance for organisms; it is found in the earth&#39;s crust in un-isolated form, and there is no substitute for it at least in flora and fauna and in living organisms. Phosphorus is for example required for the production of food, as fertilizer for plant growth, and in industry, for example in iron and steel production. Phosphorus is extensively used in particular in agriculture. 
     Even if it seems that the natural occurrence of phosphorus will not be exhausted for many decades, extensive efforts are in progress to recover phosphorus. Recovering phosphorus from waste water is of particular importance here. 
     There are many methods for recovering phosphorus, for example from sludge water by adsorption, precipitation, crystallization or using pellets, or from digested sludge by means of or without leaching, or from ash by thermal treatment thereof. 
     DE 101 12 934 B4 indicates a method in which digested sludge is aerated to increase its pH value by CO 2  stripping, in order to precipitate MAP while adding magnesium chloride at the same time. 
     The same principle is applied in accordance with EP 2 028 161 B1. To do so, a reaction tank is used in which sludge is guided in a cycle. Precipitated MAP crystals collect in a floor area of funnel-shaped design, in order to then be extracted via an extraction device shuttable on two sides. 
     DE 10 2008 050 349 B4 describes a method for precipitation of phosphorus from phosphate-contaminated waste water while forming MAP crystals. The waste water first passes through an anaerobic stage, and is then mixed with air in a stripping stage and subsequently mixed with magnesium chloride in a crystallization stage. The MAP pellets forming are removed from the floor of the reactor. 
     From JP 2004305991 A, a device and a method are known for recovering magnesium ammonium phosphate (MAP) which is/are used in waste water and sewage sludge treatment. The waste water containing the sludge is mixed with air and magnesium chloride. The heavy MAP particles are passed into a lower funnel of the device and extracted from there via a pipe. 
     The reference Stumpf, D., “ Phosphorrecycling durch MAP - Ausfällung im kommunalen Faulschlamm ”, 2007, 32 S. URL: https://www.umweltbundesamt.de/publikationen/phosphorrecycling-durch-map-faellung-im kommunalen-faulschlamm (retrieved on Nov. 7, 2018), offers an overview of existing methods for phosphorus recycling by MAP precipitation and for separation of the precipitation product. Conventionally, this takes place after the anaerobic treatment of sewage sludge and/or primary sludge. MAP precipitation is as a rule performed in precipitation reactors or fluidized-bed reactors in which the pH value is increased by alkali addition or by air stripping, and with or without the addition of magnesium precipitants. MAP is conventionally precipitated directly from the digested sludge or from the process water of sludge dewatering. The precipitated MAP can be separated using screens, hydrocyclones or centrifuges. 
     The object underlying the present invention is to develop a method and an arrangement of the type mentioned at the outset such that a high phosphorus recovery rate is enabled. 
     To solve the object, the method substantially proposes that sludge is supplied from the first reactor tank to a second reactor tank in which an anaerobic environment is set for phosphorus redissolution, and that magnesium ammonium phosphate crystals precipitated in the second reaction tank are supplied to the first reaction tank. 
     In accordance with the invention, a method is proposed which uses two reaction tanks, which are set differently in respect of their environment such that there is an aerobic environment in the first tank and an anaerobic environment in the second tank. The latter permits phosphorus redissolution. 
     The sludge discharged from the first reaction tank is supplied to the second reaction tank. 
     If bacteria contained in the digested sludge have absorbed more phosphate in the first reaction tank under aerobic conditions parallel to orthophosphate crystallization, phosphorus redissolution can take place under anaerobic conditions in the second reaction tank, leading to further MAP crystal formation or to crystal growth. Crystal formation also includes here microcrystals, which are supplied to the first reaction tank as seed crystals. 
     It is possible that sludge, basically a sludge/water mix, is extracted continuously or in batches from the preferably conically designed floor area of the second reaction tank and returned to the first reaction tank. Recirculation takes place. 
     In accordance with the invention, a cycle is formed in which the first and second reaction tanks are located, to supply from the first reaction tank to the second reaction tank sludge or a sludge/water mix of which at least part is returned to the first reaction tank, i.e. recirculated. 
     Discharge from the second reaction tank is achieved in particular using an extraction pump. 
     The inflowing sludge/water mix, for simplicity&#39;s sake referred to as sludge, which is not recirculated into the first reaction tank, optionally passes, for example via an extraction pump, to a separator in which MAP crystals are separated, which are then supplied to the first reaction tank. The separator is in particular a cyclone separator, such as a hydrocyclone. 
     There is however also the possibility that the sludge/water mix taken from the second reaction tank and not recirculated into the first reaction tank bypasses the optionally connected separator in order to be subjected directly to dewatering. 
     According to the prior art, it is provided that the pH value in the first reaction tank is set by CO 2  stripping with simultaneous dissolving of O 2 . The latter creates an aerobic environment. 
     The carbon dioxide is stripped out by fine-bubble, medium-bubble or large-bubble pressure aeration in the first reaction tank, so that the pH value is set, i.e. increased, as already mentioned. By contrast, only a weak agitation movement is performed in the second reaction tank, allowing an anaerobic environment to form and thereby permitting the redissolution of orthophosphate. As a result, further MAP crystals can form in the second reaction tank, which include so-called microcrystals and are conveyed as seed crystals or crystal nuclei into the first reaction tank. 
     Crystal growth takes place in the first reaction tank, by the microcrystals growing into macrocrystals. By contrast, it is substantially microcrystals that form inside the anaerobic second reaction tank due to redissolution. 
     Microcrystals are used to grow large crystals, because microcrystals have a size or weight which mean that it is only with great difficulty that they can be separated from the sludge, if at all, using the standard separation techniques. By contrast, macrocrystals can be readily separated from the sludge. 
     For aeration of the sludge or sludge/water mix in the first reaction tank, it is provided that the first reaction tank is split into an upper section and a lower section, where the lower section should have a conical shape and merge into the extraction device for MAP crystals. The upper section is cylindrical and is split into an inner area and an outer area by a partition wall forming a circle in its cross-section, so that an inner cylindrical area and an outer circular-cylindrical area are created. 
     The partition wall, which can also be referred to as a cylindrical shaft fitting, starts in the upper area of the first reaction tank below the sludge level and ends in the lower area at the transition between the upper section and the lower section having a conical shape. Accordingly, the first reaction tank is split into three areas, i.e. an inner cylindrical area, a cylinder ring-shaped outer area, and the conical lower section. 
     The sludge is aerated in the interior of the cylindrical inner area, in particular by membrane aerators. It is provided here in particular that inside the inner area along the height of the reaction tank, aerating elements such as membrane aerators are arranged either only in the lower area or on two levels at a distance from one another. 
     The introduction of air via the aerating elements serves the following purposes:
         Mixing in the first reaction tank and/or creation of a directed flow profile of the sludge or sludge/water mix,   Grading of MAP crystals,   Gas exchange in the sludge/water mix for CO 2  stripping.       

     Mixing in the first reaction tank and creation of the desired directed flow of the sludge or sludge/water mix in the inner area of the reaction tank by the introduction of air take place due to the resultant density difference between the “heavier” medium in the unaerated outer cylinder ring section and the “lighter” medium in the aerated inner area, and by the expulsion force of air bubbles and the uplift force initiated thereby. Due to the uplift force of the added air bubbles, the sludge/water mix is sucked in from the cylinder ring section below the partition wall between the inner and outer areas to the middle of the tank, permeated with air, and then driven in the uplift direction inside the inner area in a vertical flow to the sludge surface. At the surface, the sludge/water mix then degasses and flows horizontally above the partition wall and outwards to the peripherally extending cylinder ring section. This is followed by the vertical downward movement in the outer unaerated cylinder ring section in the direction of the tank floor, i.e. the lower section having a conical shape. 
     The driving force in the cycle described is the energy input by adiabatic compression of air in a compressor and by subsequent polytropic expansion following introduction to the sludge/water mix. 
     The uplift force in the interior of the cylindrical area is also set by the energy input. This results in grading of the MAP crystal size, because the bigger the crystal structure, the greater its weight and accordingly its gravity-related sedimentation rate. Above a certain size and hence weight of the crystals, the uplift force is no longer sufficient to carry the crystals into the vertical upward flow in the cylindrical inner area, with the result that the crystals sediment in the lower area, i.e. in the conical lower section, and settle there. 
     By contrast, small crystals, i.e. those with low weight, can be carried along with the flow, so that they remain inside the process cycle until they grow to a size such that the weight of the crystals cannot be overcome by the uplift forces, with the result that they settle in the lower area. 
     The introduction of air in the lower area of the interior of the upper section of the first reaction tank also leads to stripping of CO 2  from the sludge/water mix. Dissolved carbon dioxide can be separated by the outflowing air and degasses at the sludge surface together with the air. At the same time, oxygen is added, making the environment aerobic. 
     The pH value increase achieved by stripping initiates, as magnesium is simultaneously provided by metering of in particular magnesium chloride or another suitable magnesium compound, MAP crystal formation or crystal growth. 
     The first reaction tank is supplied with sludge into the inner aerated area at the sludge level. The cationically bonded magnesium, in particular in the form of magnesium chloride, is metered onto the sludge surface preferably via the cylinder ring-shaped outer area. 
     In particular, it is provided that the sludge or the sludge/water mix is extracted from the outer cylinder ring section. It is therefore provided in an embodiment that there is a discharge shaft in the outer area of the upper section of the first reaction tank. Discharge should take place according to the positive displacement principle. When the first reaction tank is supplied with sludge, sludge in the same volume proportion is simultaneously washed out of the reaction tank. Displacement from the lower area of the outer cylinder ring section is into a discharge duct. Discharged sludge/water mix initially flows upwards in the discharge duct, starting from the floor area of the outer area, and over a discharge sill into an outlet area. The sludge/water mix discharge is then passed from the first reaction tank into the second reaction tank. 
     The second reaction tank is mixed to a minor extent without however being aerated. This creates the required anaerobic environment conditions, so that phosphorus redissolution can take place, leading as already mentioned to further MAP crystal formation or growth. The crystals thus created collect in the lower area, also designed in particular conical, of the second reaction tank so that they reach the first reaction tank by continuous or intermittent extraction of the sludge/water mix quantity. Recirculation of the sludge or sludge/water mix quantity follows. 
     The discharge from the second reaction tank is achieved by means of an extraction pump from the upper cylindrical tank part above the agitator. 
     In an embodiment of the invention, it is provided, that the digested sludge is optionally slightly acidified by the addition of acid before being supplied to the first reaction tank, in order to increase the orthophosphate concentration for intensification of subsequent MAP crystallization in the inflow to the first reaction tank. 
     An arrangement for recovering magnesium ammonium phosphate from sludge comprising a first reaction tank with a cylindrical upper section having an inner area and an outer area and merging into a lower section having a conical shape and from which section extends in turn an extraction device for magnesium ammonium phosphate crystals, at least one aeration device being provided in the inner area of the upper section, is characterized in that the arrangement has a second reaction tank which is connected to the first tank to form a sludge-bearing cycle. It is provided here that a first line leading to the second reaction tank extends from a discharge of the first reaction tank, and a second line leading to the first reaction tank extends from the floor area of the second reaction tank. 
     In an embodiment of the invention, it is provided that the second reaction tank is optionally connected via an extraction pump to a separator, such as a cyclone separator, that separates magnesium ammonium phosphate crystals, which is connected via a third line to the first reaction tank and/or via a fourth line to the second reaction tank and via which MAP crystals can be supplied to the first reaction tank and/or to the second reaction tank. 
     In particular, it is provided that inside the inner area of the first reaction tank one or more aeration devices are arranged either only in the lower area or on two levels at a distance from one another over its height. 
     Furthermore, an infeed for cationic magnesium should lead to the sludge surface, preferably via the outer area of the first reaction tank designed in cylinder ring shape. 
     In an embodiment, it is provided that the first reaction tank is connected to a sludge supply line which is optionally connected to a pre-acidification device. 
    
    
     
       Further details, advantages and features of the invention can be gathered not only from the claims and in the features to be found therein, singly and/or in combination, but also from the following description of preferred examples to be found in the drawing. 
       The drawing shows in: 
         FIG. 1  an illustration of the principle of an arrangement for recovering magnesium ammonium phosphate, 
         FIG. 2  an illustration of the principle of a first reaction tank. 
     
    
    
     On the basis of the figures, a two-stage method in accordance with the invention is described, by means of which magnesium ammonium phosphate crystals are precipitated from digested sludge. 
     The two-stage method is explained purely in principle on the basis of  FIG. 1 . 
     Substantial components of the arrangement for recovering phosphorus, i.e. for precipitating magnesium ammonium phosphate crystals, are a first reaction tank  10  in which an aerobic environment prevails, and a second reaction tank  12  with an anaerobic environment. The first reaction tank  10  is connected via a first line  14  to the second reaction tank  12 , which in turn is connected via a second line  16  to the first reaction tank  10  for recirculation of magnesium ammonium phosphate crystals or of sludge containing crystal nuclei. This second line  16  preferably leads into a line  18  via which sludge is supplied from a sludge digestion plant to the first reaction tank  10 . 
     If required, the digested sludge can be slightly acidified by acid, for example H 2 SO 4 , before being supplied to the first reaction tank  10 , in order to increase the orthophosphate concentration for intensification of subsequent magnesium ammonium phosphate (MAP) crystallization in the inflow to the first reaction tank  10 . 
     According to the illustration of the principle in  FIG. 1 , the sludge can optionally flow through a tank  20  to which is supplied an acid, for example H 2 SO 4 , via a line  22 . If such an acidification is not required, a bypass line  24  is provided in order to permit supply of the sludge directly to the first reaction tank  10 . 
     The first reaction tank  10  consists, according to the illustration of the principle in  FIG. 2 , of an upper cylindrical section  26  and a lower conical or funnel-shaped designed lower section  28 . The funnel-shaped lower section  28  merges into an extraction device  30  referred to as a separator in which MAP crystals are collected, in order to supply them to a container  36  after opening of, for example, a rotary valve  32  or an otherwise secured outlet device via a dewatering screw  34 . The dewatering water produced during conveying via the screw  34  is extracted via a line  38 . 
     A partition wall  40  forming a ring in section is installed in the upper section of the first reaction tank and is at a distance to the outer wall  42  of the upper section  26 , such that between the partition wall  40  forming a hollow cylinder and the outer wall  42  of the first reaction tank  10  an outer area  44  ring-shaped in section is provided which equates to a cylinder ring section. The upper rim of the partition wall  40  is at a distance from the sludge level  47 . 
     On the floor side, the partition wall  40  ends just above the area in which the upper section  26  merges into the lower section  28 , as illustrated in the drawing. 
     Inside the interior  46  enclosed by the partition wall  40  are aerator devices  48 ,  50 , in particular in the form of membrane aerators, for introducing air into the interior  46 , which is filled with sludge/water mix. 
     The introduction of air must serves three purposes. The introduction of air achieves a directed flow profile of the sludge flowing inside the reaction tank  10  while mixing it. There is also a grading of the MAP crystals, as is explained in the following. Finally, there is a gas exchange in the sludge, which is basically a sludge/water mix, with CO 2  stripping and redissolution of oxygen taking place. 
     Mixing in the first reaction tank  10  and creation of the directed flow in the upper part  26  of the reaction tank  10  are generated by the resultant density difference between the unaerated medium inside the outer area  44  and the aerated medium in the interior  46 , and by the uplift force of the air bubbles exiting the aerator devices  48 ,  50 . Due to the difference between the “heavy” medium in the ring-shaped outer area  44  and the “lighter” medium in the interior  46 , the sludge or sludge/water mix is drawn out of the annular area  44  to the middle of the tank, and accordingly flows around the lower rim of the partition wall  40 . 
     Inside the interior  46 , the sludge is permeated with air, in order to then be driven in the uplift direction in the interior  46  in a vertical flow to the sludge surface  47 . At the sludge surface  47 , the sludge/water mix degasses and then flows horizontally above the upper rim of the partition wall  40  and outwards to the annular area  44 . In the outer and unaerated annular area  44 , there is then a vertical downward movement in the direction of the lower section  28 . 
     The driving force in the cycle described is the energy input by adiabatic compression of air in a compressor and by subsequent polytropic expansion following introduction to the sludge/water mix. The air is supplied to the membrane aerators  48 ,  50  by means of fans  52 ,  54  via lines  56 ,  58 . 
     To enable MAP crystals to precipitate, the ammonium present in the sludge and cationic magnesium is required, which in the example is supplied in the form of magnesium chloride, onto the sludge surface  47 , preferably via the annular area  44 . In the illustration of the principle in  FIG. 1 , the magnesium chloride  5  is added via a line  60 .The energy input also sets the uplift force in the interior  46  of the upper section  26  of the first reaction tank  10 . This grades the precipitating MAP crystal size. The bigger the crystal structure, i.e. the greater the weight of the MAP crystals, the greater the gravity-related sedimentation rate. Above a defined size and hence weight of the crystals, the lifting force in the interior  46  is insufficient to carry the crystals into the vertical upward flow, with the result that the crystals fall in the direction of the lower section  28  and sediment there, collecting in the separator  30 . Smaller crystals are by contrast drawn along with the flow and carried in the process cycle until a size is reached that allows settling inside the conical or funnel-shaped lower section  28  and hence inside the separator  30 . 
     The air introduced via the membrane aerators  48 ,  50  leads to stripping of CO 2  from the sludge/water mix. This increases the pH value, in particular to a value between 7.5 and 8.2. The pH value increase initiates, as magnesium is simultaneously provided by metering of magnesium chloride or another suitable magnesium compound, MAP crystal formation or crystal growth. 
     The digested sludge itself, which is supplied via the line  18  to the first reaction tank  10 , is supplied, as shown in  FIG. 2 , at the sludge level  47  of the first reaction tank  10 . 
     There is also the possibility to introduce a defoamer for reducing foaming on the sludge surface  47 , via a line  66  or directly into the line  18 . 
     In the outer area between the partition wall  40  and the outer wall  42 , i.e. in the annular area  44 , is a discharge shaft  98  which leads into a pipe  70 , starting from which the sludge is supplied via the first line  14  to the second reaction tank  12 . 
     The discharge from the first reaction tank  10  is in accordance with the positive displacement principle. When the first reaction tank  10  is supplied with sludge, sludge in the same volume proportion is simultaneously washed out of the first reaction tank  10 . 
     The displacement is out of the lower area of the upper section  26  from the annular area  44  into the discharge shaft  98 . Discharged sludge/water mix flows inside the discharge shaft  98  upwards—in the drawing illustration matching the direction of the arrow  74 —in order to then reach the discharge area over a discharge sill  76 , as indicated by the arrow  77 . 
     The sludge or the sludge/water mix reaching the second reaction tank  12  via the first line  14  is subjected to an anaerobic environment. To ensure this, there is only gentle mixing (agitator  78 ) without any aeration. If bacteria contained in the digested sludge have absorbed more phosphate in the first reaction tank  10  under aerobic conditions parallel to orthophosphate crystallization, phosphorus redissolution leading to further MAP crystal formation or to crystal growth takes place under anaerobic conditions in the second reaction tank  12 . A predefined sludge/water mix quantity is then extracted continuously or intermittently, i.e. in batches, from the lower section  80 , also having a conical or funnel shape, of the second reaction tank  12 , whose upper area should have a cylindrical shape, and is recirculated via the second line  16  into the first reaction tank  10 , as already explained above. To do so, there is a pump  84  in the second line  16 . 
     Discharge from the second reaction tank  12  is achieved using an extraction pump  100 . Inflowing sludge/water mix which is not recirculated into the first reaction tank  10  is extracted and discharged via this extraction pump  100 . It is possible here to subject the sludge either directly to dewatering via a line  88  or optionally to pass it through a separator  90 , such as a hydrocyclone, in order to separate MAP crystals or crystal nuclei still present in the sludge, which are then supplied via a third line  92  to the first reaction tank  10  and/or passed via a fourth line  102  back into the second reaction tank  12 . These are substantially microcrystals. 
     The MAP crystals separated in the first reaction tank  10  pass into the separator  30 , which extends from the lowest point of the lower section  28  of the reaction tank  10 . 
     To free the MAP crystals from sludge particles or flocs, it is provided in accordance with the invention that connections for flushing water (connection  94 ) and flushing air (connection  96 ) are provided in the lower area of the separator  30 , whereby loosening of the MAP crystals by the introduced flushing air and washing by the introduced flushing water take place. At the same time, the MAP crystals are graded, such that large, i.e. heavy MAP crystals remain in the lower area of the separator  30  while smaller and lighter MAP crystals and sludge particles and flocs rise and are washed back into the first reaction tank  10 . Small MAP crystals are therefore returned to the previously explained process in the first reaction tank  10 , with the result that further growth can take place. 
     To return the flushed-out microcrystals and sludge flocs to the previously described process in the first reaction tank  10  after loosening up by the flushing air supplied via the connections  96  to the separator  30  and by the flushing water supplied by connections  94  or lines to the separator  30 , it is provided that the flushed-out substances are guided through the conical lower section  28  of the first reaction tank  10 . Without flowing inside it, the substances are guided vertically through the lower section  28  to the upper cylindrical section  26 . To do so, a pipe-like guide  31 , which is widened on the separator side, is provided which is an extension of the separator  30 , as indicated in self-explanatory form in the drawing illustration in  FIGS. 1 and 2 . The guide  31  with the funnel-shaped widening  33  ensures that the flushed-out substances, i.e. microcrystals and sludge flocs, directly reach the influence area of the upward-directed flow in the interior of the upper section  26  of the first reaction tank  10  enclosed by the cylindrical partition wall  40 , without any slowing down due to the widening of the flow profile inside the funnel-shaped lower section  26 , by which the uplift force would be lost. 
     In other words, the guide  31  is used to guide flushed-out substances from the separator  30  directly into the interior  46  of the upper section  26  enclosed by the cylindrical partition wall  40 . 
     Regarding the separator  30 , it should be noted that it can be designed closure-free on the tank side for its separation function. However, a closure can be provided that separates the separator from the tank, for example to perform maintenance work, for example on the connections  94 ,  96 . 
     The separator  30  can consist for example of special steel and if necessary have an anti-stick coating, in particular on the inside, or can also be designed in steel with anti-stick coating on the inside. Typical diameters of a corresponding separator  30  are between 300 mm and 600 mm with a structural length of between 400 mm and 1500 mm. 
     The guide  31  can also consist of special steel or steel and if necessary be provided with an anti-stick coating. Typical diameters should be 300 mm to 600 mm. The maximum length corresponds to the height of the funnel-shaped or conical lower section  28  of the first reaction tank  10 . Dimensioning/arrangement must be such that the MAP crystals can flow to the separator  30  without any disruption in the flow. 
     The volume of the first reaction tank  10  should correspond to 2 to 20 times the hourly volumetric inflow quantity to the first reaction tank  10 . Identical dimensions for the second reaction tank  12  are preferable. 
     Regarding the air introduced via the membrane aerators  48 ,  50 , it should be noted that the quantity should be 5 to 35 times the hourly volumetric inflow quantity into the first reaction tank  10 . 
     The metering of magnesium chloride depends on the concentration of PO4, NH4 and Mg ions in the inflowing sludge. 
     An anaerobic environment should prevail in the second reaction tank  12  in accordance with the invention. For that reason only gentle mixing takes place. The energy input by the agitator  78  should be 2-20 Watts per m 3  of the sludge/water mix. 
     If the optionally provided pre-acidification is performed, the pH value in the pre-acidification should not drop below 5.0.