Organic ammonium compositions and methods of their use and making

Abstract

Methods and systems for converting ammonium waste streams into certifiably Organic ammonium salts having a variety of uses in greenhouse gas-reducing activities are herein described. The resulting ammonium salt compositions can be used to enhance crop yield.

What is claimed is: 
     
         1 . A process for producing an ammonium salt composition from a liquid organic waste stream comprising ammonium, the process comprising the steps of:
 (a) providing a liquid organic waste stream comprising dissolved ammonium (ammonium waste stream),   (b) separating biogas from the ammonium waste stream to yield debiogased ammonium waste stream, wherein the biogas comprises one or a plurality of gases selected from: methane (CH 4 ), carbon dioxide (CO 2 ), hydrogen sulfide, (H 2 S) and hydrogen (H 2 ),   (c) removing solids from the ammonium waste stream to yield solids-depleted ammonium wastewater and isolated solids,   (d) stripping ammonia gas from the ammonium waste stream, debiogased ammonium waste stream, or solids-depleted ammonium wastewater without pH adjustment by a process of:
 (1) heating the ammonium waste stream, debiogased ammonium waste stream, or solids-depleted ammonium wastewater to a temperature above a temperature selected from 50° C. to 90° C., and 
 (2) distilling the ammonia gas released from the heated ammonium waste stream, debiogased ammonium waste stream, or solids-depleted ammonium wastewater through a distillation column using a downflow of the ammonium wastewater and upward stripping gas to yield separated ammonia gas and deammonified wastewater, 
   (e) delivering the separated ammonia gas to an ammonium scrubber comprising a bottom inlet gas port and a top vent gas port, and   (f) scrubbing ammonium from the ammonia gas in a packed bed vessel to yield an aqueous ammonium salt solution and a vent gas by:
 presenting a certifiably Organic acid solution into the packed bed vessel which traverses in a first direction through the packed bed vessel countercurrent to ammonia gas delivered to the bottom of the packed bed vessel, wherein said ammonia gas traverses through the packed bed vessel in a second direction, wherein the first direction and second directions are oriented in opposite directions. 
   
     
     
         2 . The process of  claim 1 , wherein the certifiably Organic acid solution comprises a biologically produced acid which has a pKa of between 1.0 and 6.5. 
     
     
         3 . The process of  claim 1 , wherein the certifiably Organic acid solution comprises an acid selected from: citric, malic, lactic, acetic, formic, oxalic, uric, myristiric, tartaric, ascorbic, humic, fulvic, camphorsulfonic, folic, fumaric, gallic, glycolic, lipoic, malonic, salicylic, sorbic, succinic, thioglycolic, thioacetic, propionic, butyric, sorbic, caproic, sulfuric, nitric, phosphoric, or combinations thereof. 
     
     
         4 . The process of  claim 1 , further comprising blending the aqueous ammonium salt solution with a high-nutrient plant food selected from inorganic fertilizer or organic fertilizer into a nitrogen-enriched composition, wherein the ammonium salt solution is optionally dried before blending with said high-nutrient plant food. 
     
     
         5 . The process of  claim 1 , wherein the aqueous ammonium salt solution is further concentrated by removal of a selected amount of water. 
     
     
         6 . The process of  claim 1 , wherein the stripping gas is selected from compressed air, steam, compressed nitrogen, argon, helium, carbon dioxide, carbon monoxide, hydrogen, and combinations thereof. 
     
     
         7 . The process of  claim 1 , wherein step (f) is prepared by a process comprising:
 (a) introducing a suitable acid in dry or wet form, allowed for use in organic agriculture, into an acid makeup station,   (b) optionally if a dry acid is used, adding water to the dry acid to yield a liquid acid solution,   (c) agitating the acid source to yield a homogenous acid solution, and   (d) heating the acid solution to increase the solubility of the acid in solution to form the certifiably Organic acid solution.   
     
     
         8 . The process of  claim 1 , wherein the deammonified wastewater of step (d) (2) is recycled and introduced back into the ammonium wastewater source. 
     
     
         9 . The process of  claim 1 , wherein the biogas produced in step (b) is further processed into certifiably Organic sulfuric acid by a process comprising:
 (1) delivering the biogas to a biological sulfur scrubber,   (2) adding a gas comprising air and/or oxygen to the biogas or sulfur scrubber vessel, and   (3) scrubbing H 2 S from the biogas using the aqueous stripping solution to form an aqueous certifiably Organic sulfuric acid solution and desulfurized biogas.   
     
     
         10 . The process of  claim 9 , wherein the certifiably Organic sulfuric acid solution is added to the Certifiably organic acid solution of step (f) in  claim 1 . 
     
     
         11 . The process of  claim 9 , wherein the aqueous scrubbing solution further comprises a biological scrubbing agent. 
     
     
         12 . The process of  claim 11 , wherein the biological scrubbing agent is selected from an aqueous solution comprising: monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, or mixtures thereof. 
     
     
         13 . The process of  claim 1 , wherein the pH is not adjusted prior to step (d). 
     
     
         14 . The process of  claim 1 , wherein step (d) (2) further comprises collecting the ammonia gas using a condenser column. 
     
     
         15 . The process of  claim 1 , wherein the distillation column further comprises a bubble-cap tray column which further comprises tray risers to enforce unidirectional liquid flow. 
     
     
         16 . The process of  claim 1 , wherein the total nitrogen content of the aqueous ammonium salt solution before dilution or concentration ranges from 4 to 12% (w/w). 
     
     
         17 . The process of  claim 1 , wherein the ammonium wastewater is selected from agricultural runoff, industrial runoff, agricultural waste, municipal waste, industrial waste, animal manure, human manure, food processing waste, animal butchering waste, petroleum refinery wastewater, blue crab processing wastewater, acetylene purification wastewater, soda ash wastewater, or anaerobically digested, hydrolyzed, or fermented combinations thereof. 
     
     
         18 . The process of  claim 1 , wherein during step (f), the pH and/or conductivity is monitored, and wherein when the pH and/or conductivity is outside of the range 4.2 to 6.8, additional certifiably Organic acid is introduced into the packed bed vessel. 
     
     
         19 . The process of  claim 1 , wherein the deammonified wastewater has an ammonium concentration of less than 30 mg N/L. 
     
     
         20 . The process of  claim 1 , wherein no foaming occurs during step (d). 
     
     
         21 . The process of  claim 1 , wherein step (a) further comprises adding exogenous base to the liquid organic waste stream. 
     
     
         22 . The process of  claim 21 , wherein the exogenous base is selected from NaOH, KOH, Ca(OH) 2 , NaHCO 3 , Na 2 CO 3 , or combinations thereof. 
     
     
         23 . A system for producing organic ammonium salt solution comprising:
 (a) an ammonium wastewater vessel comprising an inlet port, optionally a recycled deammonified wastewater inlet port, a biogas outlet vent port, optionally an agitation means, and an outlet port coupled to the inlet port of an ammonia stripper,   (b) an ammonia stripper comprising an inlet port from the ammonium wastewater blending vessel, one or a plurality of stripping gas inlet ports, a deammononified wastewater outlet port, a distillation column which is configured to receive fluids from the inlet port of the ammonium wastewater blending vessel at the top of the distillation column and is also configured to receive stripping gas through the one or plurality of stripping gas inlet ports, a heating means to heat the ammonia stripper to a selected temperature range, and an ammonia gas outlet port which is coupled to an inlet port of an ammonia scrubber,   (c) an ammonia scrubber comprising an inlet ammonia gas port, a vent gas outlet port, an inlet organic acids port, an aqueous ammonia salt solution outlet port, and a packed bed vessel configured to receive ammonia gas through the inlet ammonia gas port and organic acids through the inlet organic acids port and to vent excess gasses produced by the process through the outlet gas port and to release aqueous ammonia salt solution through the aqueous ammonia salt solution outlet port, and a heating means to heat the ammonia scrubber to a selected temperature range, and   (d) an aqueous ammonia solution vessel comprising an inlet aqueous ammonia solution coupled to the aqueous ammonia salt solution outlet port of the ammonia scrubber, and optionally an organic fertilizer blending outlet port.   
     
     
         24 . The system of  claim 23 , wherein the distillation column is selected from a bubble cap tray column, packed bed column, or flooded tray column. 
     
     
         25 . The system of  claim 23 , further comprising a solids removal apparatus interposed between the outlet port on the ammonium wastewater blending vessel and the inlet port of the ammonia stripper, wherein the solids removal apparatus comprises a removable mesh screen, wherein solid particles over a selected size range are collected on the mesh screen and prevented from entering the inlet port of the ammonia stripper. 
     
     
         26 . The system of  claim 23 , wherein the deammonified wastewater outlet port on the ammonia stripper is coupled to the recycled deammonified wastewater inlet port of the ammonium wastewater blending vessel. 
     
     
         27 . The system of  claim 23 , further comprising:
 (e) an organic fertilizer blender comprising an aqueous ammonia solution vessel inlet port, a high-nutrient plant food inlet port, an agitation means for blending the high-nutrient plant food with the aqueous ammonia solution, and an outlet port.   
     
     
         28 . The system of  claim 23 , further comprising:
 (f) an acid makeup vessel comprising an acid source inlet port for receiving organic acids, a water inlet port for receiving water, a means for mixing the organic acids and water, optionally a heating means to heat the acid makeup vessel to a selected temperature range, optionally a bio-sulfuric acid inlet port, and an outlet port coupled to the inlet organic acids port of the ammonia scrubber (c).   
     
     
         29 . (canceled) 
     
     
         30 . The ammonium salt solution produced by the process of  claim 1 .