Patent Publication Number: US-2011048230-A1

Title: Process for stripping and recovering ammonia from digested wastes and plant for carrying out said process

Description:
TECHNICAL FIELD 
     The present invention concerns a process for stripping and recovering ammonia from digested wastes. The invention also extends to the plant used for carrying out said process. The field of the invention is that of the treatment of animal excrements, hereinafter referred to as “slurry”, particularly coming from the pigs breedings, directed to reduce the ammonia and generally other nitrates content well below the thresholds imposed by the strictest regulations. 
     It is known how the excrements coming from animals breedings form a considerable source of dangerous pollutants for the environment, mainly due to their high ammonia content. 
     DISCLOSURE OF THE INVENTION 
     It is, therefore, the main object of the present invention to provide a process, and the relevant plant, suitable for reducing the nitrates content in the digested wastes, downstream their anaerobic digestion plant. 
     It is a further object of the invention to provide a process and a plant suitable for recovering energy and polluting products, so as to further reduce the emissions to the atmosphere. 
     It is, finally, a further object of the invention to provide a plant of the aforesaid kind, which has sufficiently reduced sizes so to be able to be installed also within the most modest farms, even though maintaining the efficiency and the effectiveness of a larger size plant. These and other objects are achieved with the process and the plant of claims  1  and  13 , respectively. Some preferred embodiments of the invention result from the remaining claims. 
     The invention offers the advantage of combining the material and energy recover with the nitrates reduction in the digested wastes, thus achieving the double effect of both reducing their ammonia content below the strictest thresholds and further reducing the polluting emissions to the atmosphere. 
     Moreover, the invention offers the advantage of being feasible also on small-scale, and therefore suitable for serving modest size plants, even though maintaining the efficiency and the effectiveness of a larger size plant. 
     A further advantage of the process and the plant of the invention resides in the optional use of the recovered energy and chemicals, as well as the employ of the process by-products (such as thermal energy and fertiliser) within the same agricultural supply chain. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       These and other objects, advantages and features result from the process and the plant of the invention, the plant being illustrated, by way of non limiting example, in the following figures, in which: 
         FIG. 1  shows the plant according to a preferred embodiment of the invention; 
         FIG. 2  shows a variant of the plant of  FIG. 1 . 
     
    
    
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     The plant illustrated in  FIG. 1 , representing a preferred embodiment of the invention, is particularly intended for achieving a reduction by 70-80% of the ammonia amount present in the excrements (slurry) of animal breedings coming from the relevant anaerobic treatment plant equipped with an electric power generation plant through endothermic engines. 
     In principle, the process of the invention carries out the aforesaid ammonia reduction by air/liquid extraction inside a counter-current contact tower and subsequent ammonia recover by absorption on sulphuric acid solution inside a scrubber, with ammonium sulphate production. 
     The plant of the invention essentially comprises three columns: column  1  devoted for stripping ammonia by means of a hot air stream, column  2  for absorbing the ammonia stripped from column  1  and column  3  as ammonia emission safety lock. The mechanical features of the two absorption column  2  and  3  are perfectly the same. 
     In addition to said columns, the plant of the invention provides a suction fan  4  for the gas phase exiting the stripping column  1 , which creates a slight depression inside said stripping column  1 , the solutions recirculation pumps from the columns, the apparatus  5  for the heat exchange on the first absorption column  2  as well as the control instrumentation for monitoring the chemical-physical parameters and the reactants storage tanks (not shown). The stripping of ammonia takes place inside column  1 , using the cooling air coming from the endothermic engines  6  producing electric power, already existing downstream the excrements anaerobic treatment. The air stream  7 , which has an average temperature of 60° C., is so canalised and conveyed to the stripping column  1 , which is fed, through pumps  8   a  and  8   b , with a slurry stream  9  coming from the anaerobic digester (not shown) and containing the ammonia to be stripped. 
     Inside the stripping column  1 , which is provided with a spherical filling body, the intimate contact between the hot air stream  7  and the ammonia contained in the slurry  9  takes place, thus obtaining the desired stripping effect. 
     In order to manage to achieve the expected result, the contact times between air and slurry are requested to be quite high. To this purpose, a low air velocity and a high hold-up are maintained inside the stripping column  1 , so as to have a slurry average residence time of about three hours. 
     Optionally, the stripping column  1  is equipped with a control pHmeter, which will be able to run a NaOH feeding in case a slurry basification should be needed. According to literature data this basification is not strictly necessary, but the dosage chance is anyway provided in case of need, settled the fact that the slurry is not perfectly the same from one situation to the other. In this case, in fact, the basification operation allows to obtain an identical result, with lower residence times in the column. 
     Afterwards, air passing through the stripping column  1  reaches the first absorption column, denoted with the reference numeral  2 , that is provided with a different kind of filling, in order to have a very high contact surface for each column meter. This allows to have a lower equivalent height for stage, thus improving the treatment effectiveness. A first sulphuric acid solution  10  circulates inside the first absorption column  2 , said first solution initially being an about 50% sulphuric acid solution and reacting with the ammonia stream  11  coming from the head of the stripping column  1  in accordance with the reaction: 
       2NH 4 OH+H 2 SO 4 →(NH 4 ) 2 SO 4 +2H 2 O  (I)
 
     Since the first absorption column  2  is provided to have a batch functioning, the sulphuric acid concentration will tend to decrease as ammonia is absorbed. Therefore, the first absorption column  2  is provided to be under pH control so that, upon reaching the value of pH=5.5, the plant performs a series of operations consisting in discharging the ammonium sulphate acid solution from said first absorption column  2  in a tank, displacing the sulphuric acid solution present in the second absorption column  3  into said first absorption column  2 , and restoring fresh 50% sulphuric acid solution in said second absorption column  3 . 
     The second absorption column  3  is provided for the emissions safety lock, so as to avoid that ammonia emission could be released into the atmosphere beyond the law thresholds. Said second absorption column  3  is identical to the previous first absorption column  2  from the constructive point of view, both geometrically and as filling body. These first and second absorption columns  2  and  3  will similarly have the same operative conditions, the only difference consisting in the fact that the ammonium sulphate production is quantitatively low in said second absorption column  3  and, therefore, a pH control is not provided. 
     The suction fan  4 , which is necessary for the functioning of the whole plant, is placed between the stripping column  1  and the first absorption column  2 , since the slight depression that results therefrom on said stripping column  1  helps the ammonia extraction. Optionally, the use of a biofilter (not shown) can be provided, said biofilter being located downstream the plant and intended for treating possible stinking aeriform fractions, possibly stripped together with ammonia. 
     Plant Operative Conditions 
     Stripping Step 
     In the considered example, the starting slurry  9  has an ammonia concentration comprised between 2,500 and 3,000 p.p.m., and the flow-rate to be treated is of 4 m 3 /h on average. Therefore, the ammonia amount in the slurry  9  turns out to be comprised between 10 and 12 kg/h, the target of the plant being to reduce this amount by 70%, that is to remove from 7 to 8.4 kg/h. 
     In the foreseen conditions, slurry  9  is recirculated into the stripping column  1  with a flow-rate of 5 m 3 /h so, with an average residence time of about three hours in the stripping stage, the slurry itself undergoes three passages on average in counter-current with the hot air  7 , while this latter is always “fresh”, that is without ammonia upon entering the column. Slurry is then discharged from an overflow into a collecting station, for being subsequently used according to the agronomic plan. Therefore, in the mass balance, there will be a slurry concentration upon entrance of about 3,000 p.p.m. as ammonia, and a slurry concentration upon exit of about 600 p.p.m. 
     Air  7  upon entrance has an average temperature of 60° C., with a flow-rate of 2,000 Nm 3 /h and a specific humidity of about 8 g/kg of dry air, considering an average wet bulb temperature of 20° C. and an average relative humidity of 60% as starting data (variable data depending on the meteorological conditions). Upon exit, said air is expected to have a temperature of 45° C. and a water content of 25 g/kg. 
     Therefore, the stripping column  1  is as follows: 
     
       
         
           
               
               
               
               
             
               
                   
                   
               
               
                   
                 Slurry 9 entrance 
                 Aeriform 11 exit 
                 Discharge 
               
               
                   
                   
               
             
            
               
                   
                 Slurry 4,000 kg/h 
                   
                 Slurry 3,956.8 kg/h 
               
               
                   
                 NH 3  12 kg/h 
                 NH 3  9.6 kg/h 
                 NH 3  2.4 kg/h 
               
               
                   
                 Air 1,728 kg/h 
                 Air 1,728 kg/h 
               
               
                   
                 Water 13.8 kg/h 
                 Water 43.2 kg/h 
               
               
                   
                   
               
            
           
         
       
     
     Other pollutants, mainly consisting of sulphurated products in the form of sulphides and mercaptans, could also be present in the aeriform stream  11  exiting the stripping column  1 . These compounds are expected to have very low concentrations, and in part they are also retained in the absorption and reduction columns  2  and  3 . 
     As already previously mentioned, in case of need the installation of a final biofilter for treating the aeriform effluent before discharging it into the atmosphere can be provided. 
     Absorption Step 
     During this step, the aeriform effluent  11  coming from the stripping column  1  is put in contact, inside a first absorption column  2 , with a first sulphuric acid solution  10 , initially having a concentration of 50% by weight, that provides to absorb ammonia from the aeriform stream  11  itself, with formation of ammonium sulphate. This leads to a progressive decrease of the amount of free sulphuric acid in the solution, which is let to circulate until when its pH will reach a value of 5.5. At this point, the ammonium sulphate acid solution is discharged. 
     Since the foreseen volume of tank  12 , in which the sulphuric acid solution is contained, is of 5 m 3 , this means that a solution at 50% by weight contains 2,500 kg of sulphuric acid, this corresponding to 25.5 kmoles of sulphuric acid. Expecting then to convert the 90% thereof into ammonium sulphate, in the final solution there will be 2,640 kg of ammonium sulphate, equal to 22.95 kmoles. 
     Considering the fact that the aeriform  11  entering the first absorption column  2  involves an ammonia flow of 9.6 kg/h, equal to 0.505 kmoles/h, and that the conversion yield is estimated at 95%, a solution replacement every about 48 hours (operatively, every about 2 days) is foreseen. 
     The mass balance relevant to air and ammonia entering into and exiting from the absorption stage  2 , assumed that the water content variation is insignificant, is therefore as follows: 
     
       
         
           
               
               
               
             
               
                   
               
               
                 Aeriform 11 entrance 
                 Aeriform 13 exit 
                 Discharge 
               
               
                   
               
             
            
               
                 NH 3  9.6 kg/h 
                 NH 3  0.42 kg/h 
                 (NH 4 ) 2 SO 4  2,640 kg/batch 
               
               
                 Air 1,728 kg/h 
                 Air 1,728 kg/h 
               
               
                   
               
            
           
         
       
     
     The neutralisation reaction (I) between ammonia and sulphuric acid is characterised by a quite high exothermy. As a matter of fact, standing the involved quantities, a heat development of 18.2 kW is produced. It is, therefore, necessary to remove this thermal contribution by cooling through the external heat exchanger  5 . Otherwise, taking into consideration a specific heat of 4.182 kJ/kg of solution, each hour of work would imply a temperature increase of about 3.3° C., assuming that the plant is completely adiabatic. 
     Final Reduction Step 
     Since the aeriform solution  13  exiting the first absorption column  2  is still contaminated with ammonia, with a foreseen concentration of about 200 mg/m 3 , a further reduction step is needed, which is carried out in counter-current to a fresh 50% sulphuric acid solution  19 , inside a second absorption column  3 , which is identical to said first absorption column  2  but without the cooling exchanger, since the developed heat is about twenty times lower and the temperature increase is negligible. 
     Thus, taking into consideration the exit data from the preceding column, assumed that the water content variation is insignificant, a mass balance as follows is foreseen: 
     
       
         
           
               
               
               
             
               
                   
               
               
                 Aeriform 13 entrance 
                 Aeriform 14 exit 
                 Discharge 
               
               
                   
               
             
            
               
                 NH 3  0.42 kg/h 
                 NH 3  0.019 kg/h 
                 (NH 4 ) 2 SO 4  130 kg/batch 
               
               
                 Air 1,728 kg/h 
                 Air 1,728 kg/h 
               
               
                   
               
            
           
         
       
     
     The 50% sulphuric acid solution, having ammonium sulphate dissolved therein, discharged from said second absorption column  3  is then returned to said first absorption column  2 . 
     The ammonia maximum concentration is foreseen to be lower than the value of 10 mg/Nm 3 , upon discharging into the atmosphere. This value has to be considered as the upper threshold, since a reduction by 95% for each stage represents an extremely precautionary value, which is achievable also with an absorption on water if conveniently cooled. In this case, the absorption on a sulphuric acid solution can be also regarded as quantitative and, therefore, the actual concentration upon discharge can be deemed to be lower than 5 mg/Nm 3 , and basically as near as its detection limit. 
     To strengthen what said above, it is worthy to remind that the method accepted for the ammonia analytical quantification in aeriform streams provides an absorption on a 0.1 normal sulphuric acid solution, that is at a concentration noticeably lower than what provided in the plant according to the present invention. 
     Equipment List 
     As better represented in  FIG. 1 , the plant of the invention comprises the apparatuses listed hereinafter, including the indication of their most significant characteristics: 
     
       
         
           
               
               
               
               
               
             
               
                   
               
               
                 ITEM 
                 COMPONENT 
                 MATERIAL 
                 INDICATIVE SIZE 
                 NOTES 
               
               
                   
               
             
            
               
                  1 
                 Stripping 
                 Polypropylene/ 
                 Ø: 1,200 mm 
                 Spheres filling 
               
               
                   
                 column 
                 Fibreglass 
                 Filling height: 4 meters 
               
               
                 15 
                 Stripping 
                 Polypropylene/ 
                 Volume: 10 m 3   
                 Diaphragm 
               
               
                   
                 column tank 
                 Fibreglass 
                   
                 overflow 
               
               
                   
                   
                   
                   
                 discharge 
               
               
                  8a 
                 Slurry 
                 Polypropylene/ 
                 Nominal rate: 10 m 3 /h 
                 IP 55 anti-jam 
               
               
                   
                 circulation pump 
                 PVDF 
                 Head: 15 meters of H 2 O 
                 open impeller 
               
               
                   
                   
                 Horizontal 
               
               
                  8b 
                 Slurry 
                 Polypropylene/ 
                 Nominal rate: 10 m 3 /h 
                 IP 55 anti-jam 
               
               
                   
                 circulation pump 
                 PVDF 
                 Head: 15 meters of H 2 O 
                 open impeller 
               
               
                   
                   
                 Horizontal 
               
               
                  4 
                 Fan 
                 Stainless steel 
                 Nominal rate: 2,500 m 3 /h 
                 IP55 non- 
               
               
                   
                   
                   
                 Head: 700 millimetres of 
                 sparking 
               
               
                   
                   
                   
                 H 2 O 
                 execution 
               
               
                  2 
                 First absorption 
                 Polypropylene 
                 Ø: 1,200 mm 
                 Raschig rings 
               
               
                   
                 column 
                   
                 Filling height: 3.5 meters 
                 filling 
               
               
                 12 
                 First absorption 
                 Polypropylene 
                 Volume: 5 m 3   
               
               
                   
                 column tank 
               
               
                 16a 
                 First absorption 
                 Polypropylene/ 
                 Nominal rate: 5 m 3 /h 
                 IP 55 
               
               
                   
                 solution 
                 PVDF 
                 Head: 15 meters of H 2 O 
               
               
                   
                 circulation pump 
                 submerged 
               
               
                   
                   
                 vertical 
               
               
                 16b 
                 First absorption 
                 Polypropylene/ 
                 Nominal rate: 5 m 3 /h 
                 IP 55 
               
               
                   
                 solution 
                 PVDF 
                 Head: 15 meters of H 2 O 
               
               
                   
                 circulation pump 
                 submerged 
               
               
                   
                   
                 vertical 
               
               
                  5 
                 Heat exchanger 
                 Glass lined or 
                 Power 20 thermal kW 
                 Surface about 
               
               
                   
                   
                 plastic 
                   
                 10 m 2   
               
               
                  3 
                 Second 
                 Polypropylene 
                 Ø: 1,200 mm 
                 Raschig rings 
               
               
                   
                 absorption 
                   
                 Filling height: 3.5 meters 
                 filling 
               
               
                   
                 column 
               
               
                 17 
                 Second 
                 Polypropylene 
                 Volume: 5 m 3   
               
               
                   
                 absorption 
               
               
                   
                 column tank 
               
               
                 18a 
                 Second 
                 Polypropylene/ 
                 Nominal rate: 5 m 3 /h 
                 IP 55 
               
               
                   
                 absorption 
                 PVDF 
                 Head: 15 meters of H 2 O 
               
               
                   
                 solution 
                 submerged 
               
               
                   
                 circulation pump 
                 vertical 
               
               
                 18b 
                 Second 
                 Polypropylene/ 
                 Nominal rate: 5 m 3 /h 
                 IP 55 
               
               
                   
                 absorption 
                 PVDF 
                 Head: 15 meters of H 2 O 
               
               
                   
                 solution 
                 submerged 
               
               
                   
                 circulation pump 
                 vertical 
               
               
                 P4 
                 Service pump to 
                 Polypropylene/ 
                 Flow-rate: 30 m 3 /h 
                 IP 55 
               
               
                   
                 H 2 SO 4  tanks 
                 PVDF 
                 Head: 30 meters of H 2 O 
                 magnetic 
               
               
                   
                   
                 horizontal 
                   
                 after-effect 
               
               
                 P6 
                 Service pump to 
                 Polypropylene/ 
                 Flow-rate: 15 m 3 /h 
                 IP 55 
               
               
                   
                 NaOH tank 
                 PVDF 
                 Head: 15 meters of H 2 O 
                 magnetic 
               
               
                   
                   
                 horizontal 
                   
                 after-effect 
               
               
                   
               
            
           
         
       
     
     Consumptions Estimate: Reagents, Electric Power and Water 
     As far as the reagents consumption is concerned, the consumption depends on the ammonia amount present in the starting slurry, on the average flow-rate of the slurry to be treated and on the stripping and absorption percentages. Therefore, starting from the design values, hereinafter summarised:
         Entering ammonia concentration: 3,000 p.p.m.   Hourly average flow-rate of the slurry to be treated: 4,000 kg/h   Stripped ammonia percentage: 80%   Converted ammonia percentage: 99%
 
an hourly consumption of 50% sulphuric acid equal to 50 kg/h is estimated.
       

     The plant estimated installed power consists of the following items: 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 ITEM 
                 POWER 
                 CHARGE PERC. 
                 OPERATION 
               
               
                   
               
             
            
               
                  8a 
                 1.5 kW 
                 80% 
                 Continuous 
               
               
                  8b 
                 1.5 kW 
                 80% 
                 Alternative to 8a 
               
               
                 16a 
                 1.1 kW 
                 80% 
                 Continuous 
               
               
                 16b 
                 1.1 kW 
                 80% 
                 Alternative to 16a 
               
               
                 18a 
                 1.1 kW 
                 80% 
                 Continuous 
               
               
                 18b 
                 1.1 kW 
                 80% 
                 Alternative to 18a 
               
               
                  4 
                 7.5 kW 
                 80% 
                 Continuous 
               
               
                 P4 
                   4 kW 
                 80% 
                 Intermittent (10%) 
               
               
                 P6 
                 2.2 kW 
                 80% 
                 Intermittent (10%) 
               
               
                 Aux 
                   3 kW 
                 80% 
                 Discontinuous (50%) 
               
               
                   
               
            
           
         
       
     
     Depending on what said above, the hourly average power absorption can be estimated to be of about 11 kW. As far as the water consumption is concerned, it is worthy to notice that water is supposed to be used just as coolant. Therefore, once carried out its duty, it can be assigned for other uses, since it does not enter in contact with any pollutants and it only changes its thermal level. 
     As already said before, the absorption reaction (I) between ammonia and sulphuric acid inside the first absorption column  2  implies a reaction exothermy, which has to be removed from the system in order to avoid a continuous temperature increase. 
     The formation enthalpies of the different species are the following:
         (NH 4 ) 2 SO 4 =1,181 kJ/mol   H 2 SO 4 =814 kJ/mol   NH 4 OH=46 kJ/mol   H 2 O=286 kJ/mol
 
and being the produced ammonium sulphate equal to 0.242 kmols/h, the following balance is obtained:
   ΔHr=[0.242×1,181−(0.483×46+0.242×814)]×1,000   ΔHr=65,530 kJ/h equal to 18.2 kW of thermal power.       

     Since the specific heat of water is 4.182 kJ/kg, and accepting a ΔT of 5° C., a water consumption of 3.2 m 3 /h ensues. 
     Taking into account the farm self-consumption needs, a closed-circuit plant can be considered, said plant having an evaporative tower and using the sole cleansing for the firm internal consumption. Other possible cooling methods could be taken into consideration depending on the firm internal availabilities. 
     Making now reference to  FIG. 2 , a variant of the plant for stripping and recovering ammonia from digested wastes according to the present invention is shown. 
     In particular, according to said variant, the plant further comprises:
         a heat exchanger  20 , placed on the slurry recirculation line  9  into the stripping column  1 ;   a heat recoverer  26 , placed between the endothermic engines  6  and the stripping column  1 ; and   a condenser  27 , placed on the head exiting line from the stripping column  1 , before entering the first absorption column  2 .       

     Said heat recoverer  26  allows to use the hot air stream  7   a  coming from the endothermic engines  6  for heating the ambient air stream  21   a ; the air stream  7   b  coming from the endothermic engines, cooled, can be released directly to the atmosphere, while the ambient air stream  21   b , heated, is sent into the stripping column  1 . 
     The use of said heat recoverer  26  allows to avoid to send into column the air coming from the endothermic engines  6 , rich of CO 2 , with consequent saving of sodium hydroxide NaOH for maintaining the pH value of the solution in the stripping column  1 . 
     Said condenser  27  allows to reduce the water amount present in the stream  22   a  exiting the stripping column  1 , generating a stream  22   b  entering the first absorption column  2  having a smaller water amount and a condensate stream  25 ; condensation takes place by means of two streams  23   a  and  24   a , of cold water, at about 20° C., and of chilled water, at about 10° C., respectively, entering said condenser  27 , streams  23   b  and  24   b  forming the corresponding streams exiting said condenser. 
     The use of said condenser  27  allows to remove a part of water that is present in the stream exiting the stripping column  1  before entering the first absorption column  2 , this avoiding to dilute the ammonium sulphate below 30%, said dilution depending on the water amount both upon entrance into and upon exit from the second absorption column  3 . 
     The employ of known apparatuses commonly used in the technical field, as an alternative and/or in addition to those provided by the embodiments herein shown, suitable for optimising the functioning of the plant according to the invention in terms of, for instance, energy saving and/or chemicals saving, is part of the scope of the present invention.