WO2004094024A2 - Process for regenerating a spent sorbent - Google Patents
Process for regenerating a spent sorbent Download PDFInfo
- Publication number
- WO2004094024A2 WO2004094024A2 PCT/US2004/012828 US2004012828W WO2004094024A2 WO 2004094024 A2 WO2004094024 A2 WO 2004094024A2 US 2004012828 W US2004012828 W US 2004012828W WO 2004094024 A2 WO2004094024 A2 WO 2004094024A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sorbent
- solution
- acid
- flue gas
- gas stream
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
Definitions
- This invention relates to the removal of mercury and other pollutant species from flue gas streams generated during the burning of fossil fuels.
- this invention is drawn to a process and system for regenerating spent sorbents, or enhancing fresh sorbents.
- Burning fossil fuels such as coal generates a flue gas that contains contaminants including mercury and other trace elements.
- the flue gas contains oxides of sulfur and nitrogen (acid gas emissions) and particulates whose release to the environment must be controlled by use of sorbents, scrubbers, filters, precipitators, and other removal technologies.
- mercury is generated in its' elemental form during combustion. Downstream of the boiler, in the ducts and stack of the combustion system, part of the elemental mercury is oxidized. The amount of mercury oxidized depends on the amount of hydrochloric acid (HC1) and other gases present in the flue gas.
- HC1 hydrochloric acid
- the amount of mercury in a gas stream varies with different coal, but a typical concentration of mercury in the stream of combustion gas is about 5 parts per billion (ppb). As a result, several pounds of mercury per day may be emitted in some utilities.
- Another type of mercury control method uses carbon beds for mercury capture in flue gas. In these types of systems, spent sorbent is typically burned and not regenerated. Some prior art systems employ a recirculating carbon bed, where mercury is removed along with acid gases (as ammonium salts) and the carbon is regenerated at high temperatures where ammonium sulfate is decomposed to SO 2 and
- Another type of mercury control method involves injecting manganese oxide sorbent particles in a flue gas stream.
- US Patent 6,579,507 describes such a method.
- regeneration is claimed by removal of spent oxide particles from the reaction zone and rinsing with dilute aqueous acid.
- One problem with manganese oxide sorbents is that, while they do oxidize and remove elemental mercury from flue gas, the reaction rates are far slower than those with activated carbons. This means that the MnO 2 sorbent can not handle high flow rates of flue gas
- the acid wash of the MnO 2 sorbent does not restore the sorbent to its full original activity.
- the purpose of the acid wash treatment is to actually remove the poisoned and spent manganese from the surface of the sorbent as soluble salts, which destroys a portion of the sorbent.
- the soluble salts contaminate the wash solution, and it is difficult to economically separate and recover the manganese and mercury.
- U.S. Pat. No. 5,607,496 teaches the oxidation of mercury on a metal oxide sorbent bed and subsequent absorption to a sorbent.
- the sorbent bed follows the particulate removal equipment and thus the gas still contains the SO x and NO x , which
- US Patent 6,596,661 describes the regeneration of a plate or honeycomb material composed of transition metal oxides that was used for sorption of mercury in flue gas.
- the claimed process involves heating the sorbent in a reducing gas stream to remove poisons, followed by impregnation with a poly functional complex-forming reagent containing the catalyst active component to restore mercury capture capacity.
- the first of these steps can remove the mercury, but it is unclear whether it actually removes the sulfate poison.
- the second of these steps is rather expensive, because one is actually reconstituting the reagent on the sorbent.
- Examples include peroxomonosulfate (for example, US Patent 4,786,483), triiodide or other mixed halogens (for example, US Patents 3,194,629 and 3,662,523), and sulfur (for example, US Patents 3,194,629; 4,101,631, 4,708,853, and 6,258,334).
- the reagent material is destroyed either by reaction with the flue gas during sorption or by attempts to regenerate the sorbent. Therefore, these sorbents are not regenerated, except by reimpregnation of the expensive reagent.
- Amalgamating noble metals (gold, silver) on a suitable support can be regenerated by microwave heating (for example, US Patent 6,136,072), but are expensive and not especially active for sorption in flue gas.
- An apparatus and method is provided for regenerating used sorbents by exposing used sorbents to a solution to remove contaminants collected on the sorbent.
- An apparatus and method is also provided for enhancing the effectiveness of a sorbent by exposing the sorbent to a solution that increases the sorbent effectiveness.
- the solution used is an aqueous acidic solution.
- FIG. 1 is a block diagram illustrating one example of the application of the sorbent regeneration technology of the present invention.
- FIG. 2 is a block diagram illustrating another example of the application of the sorbent regeneration technology of the present invention.
- FIG. 3 is a block diagram illustrating a process for enhancing the effectiveness of a sorbent.
- the present invention relates to the process for the removal of mercury and other pollutant species from flue gas streams generated during the burning of fossil fuels, such as in a coal-fired utility.
- This removal process utilizes a sorbent to remove pollutants from the flue gas stream, which is at the same time interacting with other flue gas components that result in poisoning or deactivating the sorbent and reducing its capacity or reaction rates with the pollutant species.
- the present invention provides a cost effective way to capture the pollutants by utilizing a process to regenerate the reactivity and capacity of the sorbent.
- a process of the present invention includes washing a used sorbent with agents selected to remove the anions that collect on the sorbent during exposure to flue gas and which poison the binding sites for mercury or other contaminants.
- the process also impregnates the sorbent with agents that promote the chemisorption of mercury and other contaminants in the next service cycle of the sorbent. This is achieved by the fact that, following or during the removal of the sulfate or other contaminants, the sorbent is washed with a reagent that restores mercury or other contaminant sorption effectiveness of the sorbent.
- the invention applies to regeneration of a sorbent in a powdered form that has been injected into a flue gas stream after particulates have been removed, and have been collected on a filtration device or ESP device.
- composition of sorbents examples include activated carbon, a metal oxide or metal oxides, a precious metal, or a composite of any of these.
- the sorbent may take the form of powdered, granulated, or fibrous carbon. Other examples are also possible.
- sorbent is used with a sorbent bed, rather than being injected.
- a sorbent bed may be a fixed bed, traveling bed, or a travelling fiber filter. In either type, the poisoning contaminants from the flue gas are removed and a promoting agent added to restore mercury sorption activity. This process of promoting the activity of the carbon itself contrasts with the earlier more expensive art of adding a reagent (such as peroxide, gold, triiodide, etc.) to the sorbent.
- a reagent such as peroxide, gold, triiodide, etc.
- the basic sorbent site can be removed from the sorbent by washing with aqueous hydrochloric acid (HCl) or excess of chloride ion to exchange the sulfate or hydrogen sulfate ions. Washing with an acid or salt solution is more effective than washing with water since the anions exchange the sulfate bound to the sorbent sites. Other acids or reagents will also exchange these ions. Washing with hydrochloric acid and/or other acids also has the effect of promoting the subsequent oxidation of elementary mercury when the sorbent is returned to service. Adding the proton from the acid to a basic carbene site on the carbon edge structure forms a carbocation that accept electrons from the neutral mercury atom forming the oxidized mercury species that is bound to the sorbent surface.
- HCl hydrochloric acid
- the solution includes one or more inorganic acids such as hydrochloric acid (HCl), hydrobromic acid (HBr), and hydroiodic acid (HI).
- the solution includes one or more salt solutions.
- the salt solution may include a halide salt, containing an associated cation, such as ammonium, sodium, potassium, iron, aluminum, boron, zinc, manganese, magnesium, calcium.
- the solution includes an organic acid, such as citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, formic acid, and acetic acid.
- the solution includes an organic salt solution.
- An organic salt solution may include at least one anion from at least one of citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, formic acid, and acetic acid, and at least one associated cation, such as ammonium, sodium, potassium, iron, aluminum, boron, zinc, manganese, magnesium, or calcium.
- the solution includes a compound comprised of a halogen combined with a Group N or Group NI element such as phosphorus, oxygen, sulfur, selenium, nitrogen, etc.
- the compound includes one or more of thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus oxychloride, hypochlorous acid, and chlorine.
- the compund includes one or more of thionyl bromide, sulfuryl bromide, phosphorus tribromide, phosphorus oxybromide, hypobromous acid, and bromine.
- water can be used to wash much of the sulfuric acid and sulfates off a carbon sorbent.
- this treatment may only be effective in restoring the activity of the sorbent for capture of elementary mercury if halogens are already incorporated into the carbon during a pretreatment or during a previous regeneration cycling of the carbon, which was carried out with a hydrohalide acid (HX).
- HX hydrohalide acid
- the present invention may also include washing the recovered powdered sorbent or the bed material in a solution of the contaminant removal agent, for example, an acid reagent. Washing with the reagents will exchange the flue-gas derived sulfate ions and other contaminants from the binding sites on the sorbent.
- the invention may also include the impregnation of agents into the'sorbent to promote sorption activity. This may be accomplished using promoters such as a protonic hydro halide acid HX or Lewis acid MeX n . These reagents enhance metal oxidation activity by creating cationic character on the carbon edge structure that attracts mercury atoms and extracts electrons from said mercury atom.
- the invention may use a reagent that promotes oxidation via chlorination of a sorbent surface, such as SOCl 2 , SO 2 Cl 2 , PC1 3 , POCl 3 , HOC1, NaOCl, Cl 2 , and
- reagents can be liquid, vapor or solution reagents, depending on their stability.
- the slurry of treated sorbent particles is subjected to a dewatering step (for example, centrifugal-based, gravity-based, or filtration-based methods) to remove the sorbent particles from the aqueous acid.
- a dewatering step for example, centrifugal-based, gravity-based, or filtration-based methods
- the sorbent is further dried via a mild thermal treatment before returning to service.
- this step will make the powdered or moving particle sorbent easier to handle during duct injection or in a contactor unit.
- Moisture may also block the pores preventing gas phase diffusion of elemental mercury, or may promote the sorption and subsequent oxidation of SO 2 to
- the water produced in the dewatering step may be treated in a settling basin with a Ca or Mg salt to produce insoluble Ca or Mg SO4, or other insoluble salt of the contaminant, which is removed as a sludge or solid.
- suitable Ca or Mg salts include lime, halide, or solutions spent from the resin regeneration step.
- the treated water may also be further subjected to treatment with a cation exchange resin in the proton form to remove any excess of Ca or Mg in the water from the settling basin and replace it with hydrogen ions.
- the resulting solution is then fundamentally what is required of the carbon regeneration step (exchange out the contaminant and add the promoter acid).
- the spent cation exchange resin from the process is treated with a protonic acid, such as HCl, to regenerate the resin in the proton form and produce a soluble Ca or Mg salt.
- a protonic acid such as HCl
- This process may include the addition of the Ca and Mg brine from the resin regenerating unit to the settling tank to aid the precipitation of the insoluble Ca or Mg salt of the contaminant.
- the process may also include the addition of acid or salt to the recycled water from the resin treatment step as needed to increase concentrations to those required for contaminant removal and promotion of sorbent activity.
- the waste water solution from the dewatering step can be simply disposed of by adding to scrubber slurry, if available, or using other disposal methods. This will convert the contaminant to insoluble calcium salts as scrubbers are designed to do.
- a regenerated or enhanced sorbent can be improved by use of an additive mixed with the sorbent prior to injecting the regenerated sorbent into a flue gas stream.
- the additive can be a calcium-based additive which functions to neutralize acids.
- the carbon sorbents were initially tested in a heated bed where a synthetic flue gas stream containing elemental mercury (11 ⁇ g/m 3 ) was passed through the bed. Concentrations of total and elemental mercury in the effluent gas were determined using a PSI Sir Galahad mercury continuous emission monitor (CEM). The powdered sorbent was supported on a quartz filter during the test, and the other sorbents were tested as a triple layer. A comparison of the original FGD powdered carbon sorbent with the sorbent after regeneration by washing with 0.1 N HBr, collecting the powder by centrifugation, and drying, revealed that the mercury capture activity was increased from an initial capture efficiency of about 50% of the mercury in the inlet to 100% capture.
- CEM PSI Sir Galahad mercury continuous emission monitor
- FIG. 1 is a block diagram illustrating one example of the application of the sorbent regeneration technology of the present invention.
- FIG. 1 should not be considered limiting, but rather depicts an exemplary system for incorporating the technology.
- FIG. 1 The process illustrated in FIG. 1 is laid out around the sorbent regeneration and treatment process 10 that, as a minimum, contacts the sorbent materials with the aqueous chemical reagent. This step could also include stronger agitation or grinding balls to expose fresh surfaces.
- Fresh sorbent and used sorbent are fed from separate storage silos 12 and 14 and metered at rates dependent upon mercury control feedback from the treated flue-gas.
- a contact reactor receives a mixture of fresh and used sorbent and facilitates the sorbent regeneration and treatment process 10. In one example, the mixture includes about 80 percent used sorbent and 20 percent fresh sorbent. Of course, other ratios can also be used. In one example, used sorbent is regenerated without using fresh sorbent.
- the sorbent mixture is exposed to an aqueous acidic solution to restore mercury sorption effectiveness to the used sorbent, as described above.
- the resulting slurry is passed through an initial dewatering process 16 (e.g., via a hydroclone, vacuum filter, settling tank, heat exchanger, or other device) to remove sorbent particles from the aqueous acidic solution.
- the dewatering process 16 is followed by a final drying process 18 that utilizes hot process gas to bring the regenerated sorbent to a point of apparent dryness to allow subsequent handling and injection into the power system for mercury control.
- the majority of the aqueous solution from the dewatering process 16 is sent back to the regeneration reactor (via the path shown by arrow 20) along with a make up stream 22 comprised of water and fresh chemical reagent.
- a portion 24 of the aqueous solution is also sent to a system 26 that uses lime addition in a settling tank 28 and ion exchange (via ion exchanger 30) to remove sulfates prior to reuse.
- the economics may favor replacing the sulfate removal step with a simple blow down stream and increased use of fresh aqueous chemical reagent (described below).
- the wet sorbent can be injected back into a flue gas stream, where it will almost instantly dry.
- FIG. 2 is a block diagram illustrating another example of the application of the sorbent regeneration technology of the present invention.
- FIG. 2 is similar to the block diagram shown in FIG. 1, with a few differences.
- FIG. 2 shows an ash separation system 32, which separates fly ash from the used sorbent.
- FIG. 2 shows storage silos 12 and 14 for providing fresh and use sorbent to a contact reactor.
- the contact reactor receives the mixture of fresh and used sorbent and facilitates the sorbent regeneration and treatment process 10.
- the resulting slurry is passed through a dewatering process 16 and drying process 18.
- Some of the aqueous solution from the dewatering process 16 is sent back to the regeneration reactor (via the path shown by arrow 20) along with a make up stream 22, as is described above.
- a portion 24 of the aqueous solution is also sent to a system 26 that uses lime addition in a settling tank 28 and ion exchange (via ion exchanger 30) to remove sulfates prior to reuse.
- the economics may favor replacing the sulfate removal step 34 with a simple blow down stream (shown as "Option A" in FIG. 2) and increased use of fresh aqueous chemical reagent.
- FIG. 3 is a block diagram illustrating a process for enhancing the effectiveness of a sorbent.
- FIG. 3 is similar to FIG. 2, without a source of used sorbent.
- FIG. 3 shows storage silos 12 for providing fresh sorbent to a contact reactor.
- the contact reactor receives the fresh sorbent and facilitates the sorbent treatment process 10, which will enhance the effectiveness of the sorbent. The remainder of
- FIG. 3 is the same as FIG. 2.
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Abstract
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Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04750664.7A EP1624963B1 (en) | 2003-04-23 | 2004-04-23 | Method of removal of mercury and other pollutant species from flue gas streams generated during the burning of fossil fuels |
| US10/554,018 US8173566B2 (en) | 2003-04-23 | 2004-04-23 | Process for regenerating a spent sorbent |
| CN200480017704.4A CN1826175B (en) | 2003-04-23 | 2004-04-23 | Process for regenerating a spent sorbent |
| CA2523132A CA2523132C (en) | 2003-04-23 | 2004-04-23 | Process for regenerating a spent sorbent |
| PL04750664T PL1624963T3 (en) | 2003-04-23 | 2004-04-23 | Method of removal of mercury and other pollutant species from flue gas streams generated during the burning of fossil fuels |
| US13/425,288 US8440585B2 (en) | 2003-04-23 | 2012-03-20 | Process for regenerating a spent sorbent |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46486803P | 2003-04-23 | 2003-04-23 | |
| US60/464,868 | 2003-04-23 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/554,018 A-371-Of-International US8173566B2 (en) | 2003-04-23 | 2004-04-23 | Process for regenerating a spent sorbent |
| US13/425,288 Continuation US8440585B2 (en) | 2003-04-23 | 2012-03-20 | Process for regenerating a spent sorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004094024A2 true WO2004094024A2 (en) | 2004-11-04 |
| WO2004094024A3 WO2004094024A3 (en) | 2004-12-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2004/012828 Ceased WO2004094024A2 (en) | 2003-04-23 | 2004-04-23 | Process for regenerating a spent sorbent |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US8173566B2 (en) |
| EP (1) | EP1624963B1 (en) |
| CN (1) | CN1826175B (en) |
| CA (1) | CA2523132C (en) |
| PL (1) | PL1624963T3 (en) |
| PT (1) | PT1624963T (en) |
| WO (1) | WO2004094024A2 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20070167309A1 (en) | 2007-07-19 |
| CA2523132C (en) | 2012-06-05 |
| CA2523132A1 (en) | 2004-11-04 |
| PL1624963T3 (en) | 2020-05-18 |
| US20120202679A1 (en) | 2012-08-09 |
| EP1624963A2 (en) | 2006-02-15 |
| US8440585B2 (en) | 2013-05-14 |
| WO2004094024A3 (en) | 2004-12-16 |
| CN1826175B (en) | 2015-07-01 |
| EP1624963B1 (en) | 2019-11-27 |
| PT1624963T (en) | 2020-01-07 |
| CN1826175A (en) | 2006-08-30 |
| EP1624963A4 (en) | 2011-10-05 |
| US8173566B2 (en) | 2012-05-08 |
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