Patent Publication Number: US-2023158449-A1

Title: Dry sorbent injection with recirculation

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     The present application claims the priority benefit of U.S. Provisional Patent Application Ser. No. 63/281,196, filed Nov. 19, 2021, entitled DRY SORBENT INJECTION WITH RECIRCULATION, incorporated by reference in its entirety herein. 
    
    
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     The present invention is generally directed to dry sorbent injection systems and processes for removing sulfur oxides from a flue gas. 
     Description of Related Art 
     Dry sorbent injection (DSI) systems and processes are traditionally used to remove sulfur oxides and/or other pollutants from flue gas streams before releasing the flue gas to the environment. However, existing systems and processes can be inefficient and produce excess waste or by-products. What is needed is a DSI system and process that provides more efficient sulfur oxide removal and/or recovers by-products for recirculation or off-site use and sale. 
     SUMMARY OF THE INVENTION 
     In one embodiment, there is provided a process for removing sulfur oxides from a flue gas. The process comprises treating the flue gas with a dry sorbent material that reacts with at least a portion of the sulfur oxides to produce sodium sulfate particulates; introducing the sodium sulfate particulates and water into a mix tank, and dissolving the sodium sulfate particulates in the water to form a sodium sulfate solution; and introducing the sodium sulfate solution and a calcium hydroxide slurry into a reaction tank, and reacting at least a portion of the sodium sulfate solution with at least a portion of the calcium hydroxide slurry to produce a reaction mixture comprising a calcium sulfate precipitate and a sodium hydroxide solution. 
     In one embodiment, there is provided a process for removing sulfur dioxide from a thermal oxidizer flue gas. The process comprises treating the flue gas with a dry sorbent material to recover sodium sulfate; reacting at least a portion of the sodium sulfate and a calcium hydroxide slurry to produce a reaction mixture comprising a solids portion comprising precipitated calcium sulfate and a liquids portion comprising sodium hydroxide solution; and recovering the solids portion as a gypsum product, wherein the gypsum product comprises at least 99% by weight calcium sulfate. 
     In one embodiment, there is provided a process for removing sulfur dioxide from a flue gas. The process comprises treating the flue gas with a dry sorbent material to recover sodium sulfate; reacting at least a portion of the sodium sulfate and a calcium hydroxide slurry to produce a reaction mixture comprising calcium sulfate precipitate and a sodium hydroxide solution; and pre-treating the flue gas with at least a portion of the sodium hydroxide solution to remove at least a portion of the sulfur dioxide from the flue gas before treating the flue gas with the dry sorbent material. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG.  1    is a process flow diagram showing a dry sorbent injection process in accordance with one embodiment of the present invention; and 
         FIG.  2 A  and  FIG.  2 B  are schematic drawings of a mix box according to one embodiment of the present invention. 
     
    
    
     DETAILED DESCRIPTION 
     The present invention is generally directed to dry sorbent injection systems and processes for removing sulfur oxides from a flue gas.  FIG.  1    shows an exemplary dry sorbent injection (DSI) system and process  10 . The embodiment shown in  FIG.  1    includes various preferred and optional features of the DSI system and process  10 . However, it should be understood that these features may be included, or certain features may be omitted, in accordance with embodiments of the present invention. Additionally, other processes and equipment not shown or described herein may also be included as necessary or desired. 
     The system  10  generally comprises a dry sorbent material mix box  20 , one or more particulate matter collection systems  30 , a first mix tank  40  for dissolving at least a portion of the particulate matter, a second mix tank  50  for producing a calcium hydroxide (lime) slurry, a reaction tank  60  for combining and reacting the dissolved particulate matter and calcium hydroxide slurry, a solids-liquids separation device  70  for separating the solid and liquid components from the reaction tank, and a dilution tank  80  for preparing a sodium hydroxide solution that may be recirculated upstream of the mix box  20  for pre-treatment of the inlet flue gas stream and/or recycled to other processes in this or other systems. 
     Referring to  FIG.  1   , the DSI process begins with an inlet flue gas stream  12  comprising entrained pollutants, which must be at least partially neutralized and/or removed before being released to the environment. For example, the flue gas stream  12  may comprise one or more pollutants, such as sulfur oxides (SO x ), nitrogen oxides (NO x ), hydrochloric acid (HCl), heavy metals (e.g., Hg, As, Pb, Se, Ca), and/or carbon monoxide (CO). In certain embodiments, the flue gas stream comprises a waste gas from a thermal oxidizer (e.g., regenerative thermal oxidizer). Thermal oxidizers are generally used to remove hazardous air pollutants (HAPs) and volatile organic compounds (VOCs) from industrial air streams. The hydrocarbon-based pollutants are thermally combusted, and thus chemically oxidized to form CO 2  and H 2 O. Thermal combustion of the pollutants typically requires relatively high temperatures (e.g., about 500° C. to about 1200° C.), and thus the waste gas from the thermal oxidizer generally has a temperature of at least about 500° C., at least about 600° C., at least about 700° C., at least about 800° C., at least about 900° C., or at least about 1000° C. In certain embodiments, the flue gas stream has a temperature about 500° C. to about 1200° C., about 700° C. to about 1100° C., or about 900° C. to about 1000° C. However, the downstream processes for removal of sulfur oxides generally require much lower processing temperatures. Thus, the waste gas for the thermal oxidizer may be cooled such that the inlet flue gas has a temperature of about 100° C. to about 300° C., about 150° C. to about 250° C., or about 175° C. to about 225° C. 
     In certain embodiments, the flue gas is not derived from a coal combustion power plant or other combustion process (e.g., incineration, etc.) that produces fly ash. Thus, in certain embodiments, the flue gas stream is substantially free of fly ash. In certain embodiments, the flue gas stream comprises less than 1000 ppmw, less than 500 ppmw, less than 100 ppmw, less than 50 ppmw, less than 10 ppmw, or less than 1 ppmw of fly ash. 
     In certain embodiments, the flue gas stream is substantially free of halogens, such as chlorides (e.g., HCl). In certain embodiments, the flue gas stream comprises less than 1000 ppmw, less than 500 ppmw, less than 100 ppmw, less than 50 ppmw, less than 10 ppmw, or less than 1 ppmw of halogens, chlorides, and/or HCl. 
     The inlet flue gas stream  12  may be optionally pre-treated, for example, to lower the temperature of flue gas steam and/or to react and remove at least a portion of the sulfur oxides present in the inlet flue gas stream  12 . Referring again to  FIG.  1   , inlet flue gas stream  12  may be fed into an optional recirculation zone  94 , wherein a sodium hydroxide (NaOH) solution may be injected into the flue gas stream. In certain embodiments, the sodium hydroxide solution may be derived from one or more downstream processes, as described in greater detail below. Upon injection into the flue gas stream  12 , the sodium hydroxide solution may provide at least a portion of the necessary cooling to the flue gas stream, thereby lowering the temperature for further processing. For example, in certain embodiments, the inlet flue gas stream  12  fed to the recirculation zone  94  may have an initial temperature of at least about 500° C., and pre-treatment with the sodium hydroxide solution may cool the flue gas temperature to about 100° C. to about 300° C., about 150° C. to about 250° C., or about 175° C. to about 225° C. Additionally, or alternatively, the sodium hydroxide may react with at least a portion of the sulfur oxides to produce sodium sulfate, sodium bisulfate, sodium sulfite, and/or sodium bisulfite particulates, according to one or more of the following reactions: 
       SO 2 +2NaOH→Na 2 SO 3 +H 2 O
 
       SO 2 +NaOH→NaHSO 3  
 
       4 SO 2 +8NaOH→4H 2 O+3Na 2 SO 4 +Na 2 S
 
       SO 2 +2NaOH→H 2 +Na 2 SO 4  
 
       SO 3 +2NaOH→H 2 O+Na 2 SO 4  
 
       SO 3 +NaOH→NaHSO 4  
 
     Any particulates formed during the pre-treatment may be collected and removed from the flue gas stream or may be carried with the flue gas stream  19  to downstream processes as described herein. 
     The inlet flue gas stream  12  (or pre-treated flue gas stream  19 ) may be further cooled, for example in a heat exchanger (not shown), to an appropriate processing temperature (as described above) and fed into mix box  20  comprising a quantity of dry sorbent material. Additionally, or alternatively, the inlet flue gas  12  may be cooled in a heat exchanger (not shown) before being pre-treated in the recirculation zone  94 . 
     Within the mix box  20 , the flue gas contacts dry sorbent material that resides in the mix box  20  or is concurrently introduced into mix box  20  along with the flue gas stream  19 . The dry sorbent material may be any of a variety of materials capable of reacting with and/or otherwise removing pollutants in the flue gas stream. In certain embodiments, the dry sorbent material is capable of reacting with and/or removing sulfur oxides and/or other acid gasses from the flue gas stream. In certain embodiments, the dry sorbent material comprises an alkaline sorbent material selected from the group consisting of sodium bicarbonate (NaHCO 3 ), sodium carbonate (Na 2 SO 3 ), trona (Na 2 CO 3 ·NaHCO 3 ·2H 2 O), and mixtures thereof. Upon contact with the flue gas, the dry sorbent material may react with at least a portion of the sulfur oxides in the flue gas to produce sodium sulfate particulates, according to one or more of the following reactions: 
       2(Na 2 CO 3 ·NaHCO 3 ·2H 2 O)→3Na 2 CO 3 +CO 2 +5H 2 O(&gt;100° C.)  (1)
 
       2NaHCO 3 →Na 2 CO 3 +CO 2 +H 2 O(&gt;100° C.)  (2)
 
       Na 2 CO 3 +0.5 O 2 +SO 2 →Na 2 SO 4 +CO 2   (3)
 
       Na 2 CO 3 +SO 2 →Na 2 SO 3 +CO 2   (3a)
 
       Na 2 SO 3 +0.5 O 2 →Na 2 SO 4   (3b)
 
       Na 2 CO 3 +SO 3 →Na 2 SO 4 +CO 2   (4)
 
     The mix box  20  advantageously provides a reaction vessel to ensure a sufficient reaction of the sorbent material and sulfur oxides, thereby increasing the removal of sulfur oxides from the flue gas stream and conversion to sodium sulfate, as compared to traditional duct injection systems. In certain embodiments, to ensure sufficient reaction of the sorbent material and sulfur oxides in the mix box, the flue gas stream may have a residence time in the mix box of at least about 0.5 seconds, or at least about 1 second. In certain embodiments, the flue gas stream may have a residence time in the mix box of about 0.5 seconds to about 5 second, or about 1 second to about 2 seconds. 
     As shown in  FIG.  1   , in certain embodiments, mix box  20  may comprise a hopper configuration having a flue gas inlet  21  and flue gas outlet  22 . At least a portion of any particulate materials (e.g., unreacted sorbent material, partially reacted sorbent material, and/or converted sodium sulfate particulates) may be collected in the hopper portion  24  and removed from the flue gas stream or may be carried with the flue gas stream to downstream processes as described herein. Any unused or partially used sorbent material may be recycled for further use in the mix box  20 . 
     In certain embodiments, a sorbent feeder device  26  may be positioned above mix box  20  and may be configured to deposit dry sorbent material  25  into an upper opening (not shown) of mix box  20  to contact the flue gas flowing therethrough. The feeder device  26  may comprise one or more inlets  27   a  for introducing fresh dry sorbent material and/or one or more inlets  27   b  for introducing recycled sorbent material to the feeder device  26 . The feeder device may further comprise an opening or chute  28  configured to direct the fresh and/or recycled sorbent material  25  into the mix box  20 . 
     The flue gas stream  29  exiting the mix box  20  is generally depleted in sulfur oxides and enriched in carbon dioxide relative to the flue gas stream  19  entering the mix box  20 . However, the flue gas stream  29  exiting the mix box  20  will generally comprise a quantity of particulate materials entrained therein, such as unreacted sorbent material (e.g., sodium bicarbonate, trona), partially reacted sorbent material (e.g., sodium carbonate), and/or converted sodium sulfate particles. 
     The flue gas stream  29  comprising entrained particulate matter may then be fed into one or more particulate matter collection systems  30 . As shown in  FIG.  1   , in certain embodiments, the one or more particulate matter collection systems may comprise a baghouse, which may comprise a plurality of bag filters  31 , which effectively collect and remove the entrained particulate matter from the flue gas stream flowing therethrough. The removed particulate matter may generally comprise sodium carbonate and/or converted sodium sulfate particles, although unreacted sorbent material and other solids may also be collected and removed. The removed particulate manner may be directed out of the collection system(s)  30  to downstream processing via conveyor  34 , which may be a belt conveyor, screw conveyor, pneumatic conveyor, or other conveyance system. 
     The flue gas stream  39  exiting the particulate matter collection system(s)  30  is generally depleted in particulate matter relative to the flue gas stream  29  entering the collection system(s)  30 . In particular, the flue gas stream  39  exiting the particulate matter collection system(s)  30  is generally depleted in sodium sulfate and/or sodium carbonate relative to the flue gas stream  29  entering the collection system(s)  30 . The flue gas stream  39  exiting the particulate matter collection system(s)  30  may then be pumped or otherwise directed to the flue gas stack  90  to be released to the environment. 
     As shown in  FIG.  1   , in certain embodiments, at least a portion of the particulate matter collected and removed in the collection system(s)  30  may be introduced into a mix tank  40  along with a quantity of water  41 . Upon mixing in the mix tank  40 , the sodium sulfate, the sodium carbonate, and/or other solids in the collected particulate matter is substantially or completely dissolved to form an aqueous solution. In certain embodiments, the quantity of water  41  is introduced at a rate such that the aqueous solution in the mix tank  40  has a total dissolved solids concentration of about 20% by weight or less. By maintaining a total dissolved solids concentration of about 20% or less, the solids may be inhibited from precipitating out of solution. In certain embodiments, the quantity of water  41  is introduced at a rate such that the aqueous solution in the mix tank  40  has a total dissolved solids concentration of at least about 1%, at least about 5%, at least about 10%, or at least about 15% by weight and/or not more than about 20% by weight. 
     The aqueous solution comprising dissolved sodium sulfate, dissolved sodium carbonate, and/or other solids may then be pumped, or otherwise introduced into a reaction tank  60 . In the reaction tank  60 , the aqueous solution is mixed with a calcium hydroxide slurry. As shown in  FIG.  1   , the calcium hydroxide slurry may be prepared by introducing dry calcium hydroxide  52  and water  51  into a slurry tank  50 , where they are mixed to form the calcium hydroxide slurry. In certain embodiments, the water is introduced into the slurry tank at a rate such that the slurry has a solids concentration of about 20% by weight or less. In certain embodiments, when the aqueous solution and slurry are mixed in the reaction tank  60 , water  61  may be introduced to the reaction tank  60  such that the reaction mixture has a solids concentration of about 15% by weight or less. In certain embodiments, when the aqueous solution and slurry are mixed in the reaction tank  60 , water  61  may be introduced to the reaction tank  60  such that the reaction mixture has a solids concentration of at least about 1%, at least about 5%, or at least about 10% by weight and/or not more than about 15% by weight. 
     In the reaction tank  60 , calcium hydroxide reacts with sodium sulfate and/or sodium carbonate to produce a sodium hydroxide solution comprising calcium sulfate and/or calcium carbonate precipitated out as solids. In particular, calcium hydroxide reacts with sodium sulfate and/or sodium carbonate to produce calcium sulfate and/or calcium carbonate in an aqueous sodium hydroxide solution, according to one or more of the following reactions: 
       Na 2 SO 4 +Ca(OH) 2 →2NaOH+CaSO 4  
 
       Na 2 CO 3 +Ca(OH) 2 →2NaOH+CaCO 3  
 
     The reaction solution may then be fed to a solid-liquid separation system  70 , wherein the precipitated solids in the sodium hydroxide solution may be separated from the solution, and optionally recovered for further use or sale. In certain embodiments, the solid-liquid separation system  70  comprises a hydrocyclone separation system. In certain embodiments, the solids recovered from the solid-liquid separation system may be further separated (not shown) to isolate specific solid components, such as calcium sulfate. However, in certain embodiments, such additional separation is not necessary or included. The recovered solids, and particularly the recovered calcium sulfate, may be further processed, for example in a filter press  92 , to remove at least a portion of any remaining liquid content from the recovered solids. Thus, in certain embodiments, calcium sulfate (gypsum) can be recovered having a liquid content of less than about 5% by weight. 
     The calcium sulfate (gypsum) recovered according to certain embodiments of the present invention can be advantageously produced with sufficient purity to be sold and used in other industries, such as various construction materials. In particular, since in certain embodiments the flue gas is substantially free of fly ash, the recovered calcium sulfate may also be substantially free of fly ash contamination. In certain embodiments, the recovered gypsum material comprises at least 99%, preferably at least 99.9% by weight calcium sulfate. 
     The liquid effluent stream  72  from the solid-liquid separation system  70  comprising the sodium hydroxide solution may be discharged or further processed. In certain embodiments, at least a portion of the sodium hydroxide solution may be reacted with carbon dioxide, for example by introducing the solution to the carbon dioxide enriched flue gas stream or other carbon dioxide-containing stream, to produce sodium carbonate, which can be recycled or sold separately. Additionally, or alternatively, in certain embodiments, the sodium hydroxide solution may be fed to an optional recirculation zone  94  to pre-treat the flue gas stream  12 , as described above. As shown in  FIG.  1   , the sodium hydroxide solution effluent stream  72  may be directed from the solid-liquid separation system  70  to a dilution tank  80 , where water  81  may be added to dilute the solution. In certain embodiments, the sodium hydroxide solution is diluted to a concentration of about 20% by weight or less. In certain embodiments, the sodium hydroxide solution is diluted to a concentration of at least about 1%, at least about 5%, at least about 10%, or at least about 15% by weight and/or not more than about 20% by weight. The diluted sodium hydroxide stream  82  may be fed to the recirculation zone  94  for use in flue gas pre-treatment as described above. 
       FIG.  2 A  and  FIG.  2 B  depict an exemplary mix box  100 , in accordance with embodiments of the present invention, and its associated components and operation are described herein. The gas stream to be treated (e.g., flue gas) flows through duct  102  into inlet cap  120 . Inlet cap  120  comprises a gas receiving side  121  adapted to be installed onto the duct  102  and a mix box feed side  123  adapted to be installed on the inlet  122  of mix box  100 . In certain embodiments, feed side  123  may have a cross-sectional area smaller than the cross-sectional area of the receiving side  121 , and thus the velocity of the gas stream flowing through inlet cap  120  may be reduced before the gas is introduced into the chamber of mix box  100 . In certain embodiments, receiving side  121  may have cross-sectional area of about 1 ft 2  to about 10 ft 2 , or about 2 ft 2  to about 5 ft 2 . In certain embodiments, feed side  126  may have a cross-sectional area of about 2 ft 2  to about 20 ft 2 , or about 5 ft 2  to about 10 ft 2 . In certain embodiments, the ratio of the cross-sectional area of the feed side  123  to the cross-sectional area of the receiving side  121  is about 1.5:1 to about 3:1, or about 2:1 to about 2.5:1. 
     As best shown in  FIG.  2 B , inlet cap  120  may comprise one or more openings  123  (e.g., lances) formed in a top or upper surface of inlet cap  120 , through which fresh and/or recycled sorbent material may be introduced, for example, from a sorbent feeder device (not shown). The sorbent introduced through openings  123  will become at least partially entrained within the gas stream and will thus be introduced into the mix box  100  along with the flowing gas. In certain embodiments, openings  123  may be generally circular and have an inner diameter of about 1 inch to about 10 inches, or about 2 inches to about 5 inches. 
     The gas stream and entrained sorbent material flow from inlet cap  120  into mix box  100 , which generally comprises an upper portion  110  and a lower hopper portion  112 . In certain embodiments, the volume of mix box  100  (including bother upper portion  110  and lower portion  112 ) is about 200 ft 3  to about 500 ft 3 , or about 300 ft 3  to about 400 ft 3 . 
     Upper portion  110  generally comprises inlet  122  formed therein, through which the gas stream and entrained sorbent material is introduced to mix box  100 , and an outlet  124 , through which the treated gas (and a residual entrained sorbent material) exits mix box  100 . In certain embodiments, the gas stream may have a residence time in mix box  100  of about 0.5 seconds to about 5 second, or about 1 second to about 2 seconds. In certain embodiments, the upper portion  110  has a height of about 5 ft to about 20 ft, or about 8 ft to about 12 ft. In certain embodiments, the upper portion  110  has a length and/or width of about 40 inches to about 100 inches, or about 60 inches to about 80 inches. 
     Lower hopper portion  112  generally comprises one or more sloped walls configured to direct the spent sorbent material through a bottom opening of lower portion  112 . Any unused or partially used sorbent material may be collected from the bottom opening and recycled for further use, for example, by introducing the recycled material into an opening  123  of inlet cap  120 . In certain embodiments, release of the sorbent material through the bottom opening may be controlled by a knife gate  130  installed at the bottom opening. In certain embodiments, the lower portion  112  has a height of about 5 ft to about 20 ft, or about 8 ft to about 12 ft. In certain embodiments, the one or more sloped walls have an angle ( 0 ) of about 50° to about 70° relative to the surface upon which the mix box  120  resides. 
     The gas stream exiting mix box  100  via outlet  124  may be directed through outlet cap  140 . Outlet cap  140  comprises a treated gas receiving side  141  and a gas outlet side  143 . Gas outlet side  143  is adapted to connect to, and to direct the gas stream into, downstream duct  104 . 
     In certain embodiments, receiving side  141  may have a cross-sectional area larger than the cross-sectional area of the outlet side  143 , and thus the velocity of the gas stream flowing through inlet cap  120  may be increased before the gas is introduced into duct  104 . In certain embodiments, outlet side  143  may have cross-sectional area of about 1 ft 2  to about 10 ft 2 , or about 2 ft 2  to about 5 ft 2 . In certain embodiments, receiving side side  141  may have a cross-sectional area of about 2 ft 2  to about 20 ft 2 , or about 5 ft 2  to about 10 ft 2 . In certain embodiments, the ratio of the cross-sectional area of the receiving side  141  to the cross-sectional area of the outlet side  143  is about 1.5:1 to about 3:1, or about 2:1 to about 2.5:1. 
     In certain embodiments, mix box  100  further comprises a damper  118  installed within a side wall of upper portion  110 , which may be used to bleed air from or into mix box  100 . In certain embodiments, damper  118  may comprise a conduit having a cross-sectional area of about 1 ft 2  to about 10 ft 2 , or about 2 ft 2  to about 5 ft 2 . In certain embodiments, damper  118  comprises a louver configured to inhibit the external environment (e.g., rain, light, etc.) from entering mix box  100 . 
     In certain embodiments, the flue gas rate through mix box  100  is about 5,000 to about 30,000 actual cubic feet per minute (ACFM), or about 10,000 to about 20,000 ACFM. The systems and processes described herein have a number of advantages over existing dry sorbent injection applications. For example, downstream reactions of particulate matter collected from the dry sorbent process allows for the production of product quality gypsum, which may be sold or used in other industries. Additionally, recovery of sodium hydroxide solution allows for recirculation and pre-treatment of the inlet flue gas, which increases sulfur oxide removal and improves efficiency by at least partially cooling the flue gas stream before the dry sorbent is injected. 
     Additional advantages of the various embodiments of the invention will be apparent to those skilled in the art upon review of the disclosure herein and the working examples below. It will be appreciated that the various embodiments described herein are not necessarily mutually exclusive unless otherwise indicated herein. For example, a feature described or depicted in one embodiment may also be included in other embodiments, but is not necessarily included. Thus, the present invention encompasses a variety of combinations and/or integrations of the specific embodiments described herein. 
     As used herein, the phrase “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing or excluding components A, B, and/or C, the composition can contain or exclude A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination. 
     The present description also uses numerical ranges to quantify certain parameters relating to various embodiments of the invention. It should be understood that when numerical ranges are provided, such ranges are to be construed as providing literal support for claim limitations that only recite the lower value of the range as well as claim limitations that only recite the upper value of the range. For example, a disclosed numerical range of about 10 to about 100 provides literal support for a claim reciting “greater than about 10” (with no upper bounds) and a claim reciting “less than about 100” (with no lower bounds).