This application claims priority to U.S. application Ser. No. 12/599,896, which is a national stage entry of PCT Application No. PCT/US08/06082, which is a continuation-in part of U.S. application Ser. No. 11/977,843, filed on Oct. 26, 2007, which claims priority to U.S. Provisional Application No. 60/966,558, filed on May 14, 2007.
FIELD OF THE DISCLOSURE
This disclosure relates to sorbent bodies comprising activated carbon, processes for making them, and methods of using them. The sorbent bodies can be used to remove toxic elements from a fluid, such as from a gas stream. For instance, the sorbent bodies may be used to remove elemental mercury or mercury in an oxidized state from a coal combustion flue gas.
Emissions of toxins into the atmosphere have become environmental issues of increasing concern because of the dangers posed to human health. For instance, coal-fired power plants and medical waste incineration are major sources of human activity related mercury emissions. Mercury emitted to the atmosphere can travel thousands of miles before being deposited to the earth. Studies also show that mercury from the atmosphere can also be deposited in areas near the emission source.
It is estimated that there are 48 tons of mercury emitted from coal-fired power plants in the United States annually. One DOE-Energy Information Administration annual energy outlook projected that coal consumption for electricity generation will increase from 976 million tons in 2002 to 1,477 million tons in 2025 as the utilization of coal-fired generation capacity increases. However, mercury emission control regulations have not been rigorously enforced for coal-fired power plants. A major reason is a lack of effective control technologies available at a reasonable cost, especially for elemental mercury control.
One technology that has been used for controlling elemental mercury, as well as for oxidized mercury, is activated carbon injection (ACI). The ACI process includes injecting activated carbon powder into the flue gas stream and using a fabric fiber or electrostatic precipitator to collect the activated carbon powder that has adsorbed mercury. Generally, ACI technologies require a high carbon to mercury ratio to achieve the desired mercury removal level (>90%), which results in a high cost for sorbent material. The high carbon to mercury ratio suggests that ACI does not utilize the mercury sorption capacity of carbon powder efficiently. Additionally, if only one particle collection system is used, the commercial value of fly ash is sacrificed due to its mixing with contaminated activated carbon powder. A system with two separate powder collectors and injecting activated carbon sorbent between the first collector for fly ash and the second collector, or a baghouse, for activated carbon powder, may be used. A baghouse with high collection efficiency may be installed in the power plant facilities. However, these measures are costly and may be impractical, especially for small power plants.
Since water-soluble (oxidized) mercury is the main mercury species in bituminous coal flue gas with high concentrations of SO2 and HCl, bituminous coal-fired plants may be able to remove 90% mercury using a wet scrubber combined with NOx and/or SO2 control technologies. Mercury emission control can also be achieved as a co-benefit of particulate emission control. Chelating agents may be added to a wet scrubber to sequestrate the mercury from emitting again. A chelating agent adds to the cost due to the problems of corrosion of the metal scrubber equipment and treatment of chelating solution. Elemental mercury is the dominant mercury species in the flue gas of sub-bituminous coal or lignite coal, and a wet scrubber is not effective for removal of elemental mercury unless additional chemicals are added to the system. It is undesirable, however, to add additional potentially environmentally hazardous material into the flue gas system.
Certain industrial gases, such as syngas and combustion flue gas, may contain toxic elements such as cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium, in addition to mercury. Like mercury, these toxic elements may exist in elemental form or in a chemical compound comprising the element. It is highly desired that the presence of one or more of these toxic elements be substantially reduced before a syngas is supplied for industrial and/or residential use or before a gas is emitted to the atmosphere.
There is a genuine need of a sorbent material capable of removing mercury and/or other toxic elements from fluids such as flue gas and syngas, with a higher capacity than activated carbon powder alone. It is also desired that such sorbent material be produced at a reasonable cost and conveniently used.
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Embodiments of the invention relate to sorbent bodies comprising activated carbon, processes for making them, and methods of using them. The sorbent bodies can be used to remove toxic elements from a fluid, such as from a gas stream. For instance, the sorbent bodies may be used to remove elemental mercury or mercury in an oxidized state from a coal combustion flue gas.
Embodiments of the invention have one or more of the following advantages. Sorbent bodies of the invention comprising activated carbon having high specific surface area and a large number of active sites capable of sorbing or promoting sorption of a toxic element can be produced and used effectively for the sorption of toxic elements, including arsenic, cadmium, mercury and selenium. The sorbent bodies of certain embodiments of the invention are effective for sorption of not just oxidized mercury, but also elemental mercury. Further, the sorbent bodies according to certain embodiments of the invention are effective in removing mercury from flue gases with high and low concentrations of HCl alike. Sorbent bodies according to certain embodiments of the invention are also effective in removing mercury from flue gases with high concentration of SO3.
Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the invention as described in the written description and claims hereof, as well as the appended drawings.
The foregoing general description and the following detailed description are merely exemplary of the invention, and are intended to provide an overview or framework to understanding the nature and character of the invention as it is claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
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The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification.
FIG. 1 is a diagram comparing the mercury removal capability of a tested sample of a sorbent comprising an in-situ extruded metal catalyst according to the invention and a sorbent which comprises impregnated metal but no in-situ extruded metal catalyst over time.
FIG. 2 is a diagram showing the inlet mercury concentration (CHg0) and outlet mercury concentration (CHg1) of a sorbent body according to one embodiment of the invention at various inlet mercury concentrations.
FIG. 3 is an SEM image of part of a cross-section of a sorbent body according to one embodiment of the invention comprising in-situ extruded metal catalyst.
FIG. 4 is an SEM image of part of a cross-section of a comparative sorbent body comprising post-activation impregnated metal catalyst.
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Unless otherwise indicated, all numbers such as those expressing weight percents of ingredients, dimensions, and values for certain physical properties used in the specification and claims are to be understood as being modified in all instances by the term “about.” It should also be understood that the precise numerical values used in the specification and claims form additional embodiments of the invention. Efforts have been made to ensure the accuracy of the numerical values disclosed in the Examples. Any measured numerical value, however, can inherently contain certain errors resulting from the standard deviation found in its respective measuring technique.
As used herein the use of the indefinite article “a” or “an” means “at least one,” and should not be limited to “only one” unless explicitly indicated to the contrary. Thus, for example, reference to “a metal catalyst” includes embodiments having one, two or more metal catalysts, unless the context clearly indicates otherwise.
As used herein, a “wt %” or “weight percent” or “percent by weight” of a component, unless specifically stated to the contrary, is based on the total weight of the composition or article in which the component is included. As used herein, all percentages are by weight unless indicated otherwise. All ppm with respect to gases are by volume unless indicated otherwise.
The term “sulfur” as used herein includes sulfur element at all oxidation states, including, inter alia, elemental sulfur (0), sulfate (+6), sulfite (+4), and sulfide (−2). The term sulfur thus includes sulfur in any oxidation state, as elemental sulfur or in a chemical compound or moiety comprising sulfur. The weight percent of sulfur is calculated on the basis of elemental sulfur, with any sulfur in other states converted to elemental state for the purpose of calculation of the total amount of sulfur in the material.
The term “metal catalyst” includes any metal element in any oxidation state, as elemental metal or in a chemical compound or moiety comprising the metal, which is in a form that promotes the removal of a toxic element (such as cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium, or such as cadmium, mercury, arsenic or selenium) from a fluid in contact with a sorbent body of the invention. Metal elements can include alkali metals, alkaline earth metals, transition metals, rare earth metals (including lanthanoids), and other metals such as aluminum, gallium, indium, tin, lead, thallium and bismuth.
The weight percent of metal catalyst is calculated on the basis of elemental metal, with any metal in other states converted to elemental state for the purpose of calculation of the total amount of metal catalyst in the material. Metal elements present in an inert from, such as in an inorganic filler compound, are not considered metal catalysts and do not contribute to the weight percent of a metal catalyst. The amount of sulfur or metal catalyst may be determined using any appropriate analytical technique, such as mass spectroscopy.
By “in-situ extruded” is meant that the relevant material, such as sulfur and/or metal catalyst, is introduced into the material by incorporating at least part of the source material thereof into the batch mixture material, such that the formed body comprises the source materials incorporated therein.
Distribution of sulfur, metal catalyst or other materials across a cross-section of the sorbent body, or an extrusion batch mixture body, or a batch mixture material of the invention can be measured by various techniques, including, but not limited to, microprobe, XPS (X-ray photoelectron spectroscopy), and laser ablation combined with mass spectroscopy.
The methodology of characterizing the distribution of a certain material (e.g., sulfur, metal catalyst, and the like) in a certain planar cross-section of a sorbent body, or other body, is described as follows. This methodology is referred to as “Distribution Characterization Method.”
Target test areas of the cross-section of at least 500 μm×500 μm size are chosen if the total cross-section is larger than 500 μm×500 μm. The full cross-section, if less than or equal to 500 μm×500 μm, would be a single target test area. The total number of target test areas is p (a positive integer).
Each target test area is divided by a grid into multiple separate 20 μm×20 μm zones. Only zones having an effective area (defined below) not less than 40 μm2 are considered and those having an effective area lower than 40 μm2 are discarded in the data processing below. Thus the total effective area (ATE) of all the square sample zones of the target test area is:
where ae(i) is the effective area of zone i, and n is the total number of the square sample zones in the target test area, where ae(i)≧40 μm2. Area of individual square zone ae(i) in square micrometers is calculated as follows:
where av(i) is the total area in square micrometers of any voids, pores or free space larger than 10 μm2 within square zone i.
Each square zone i is measured to have an average concentration C(i), expressed in terms of moles of sulfur atoms per unit effective area for sulfur, or moles of other relevant material in the case of a metal catalyst. All C(i) (i=1 to n) are then listed in descending order to form a permutation CON(1), CON(2), CON(3), . . . CON(n), where CON(1) is the highest C(i) among all n zones, and CON(n) is the lowest C(i) among all n zones. The arithmetic average concentration of the 5% of all n zones in the target test area having the highest concentrations is CON(max). Thus: