JP2010527288A5 - - Google Patents

Description

Adsorbents containing activated carbon, production method and use thereof Cross-reference of related applications

  This application claims the benefit of priority of US patent application Ser. No. 11 / 977,843 filed Oct. 26, 2007 and US Provisional Patent Application No. 60 / 966,558 filed May 14, 2007. .

The present disclosure relates to adsorbents comprising activated carbon, methods for their production, and methods for their use. The adsorbent can be used to remove toxic substances derived from fluids such as gas streams. For example, the adsorbent can be used to remove elemental mercury from the combustion flue gas of coal.

  Since the release of toxins into the atmosphere poses a danger to human health, there are growing concerns about environmental issues. For example, coal-fired power plants and incineration of medical waste are the main causes of mercury emissions associated with human activities. Mercury released to the atmosphere travels thousands of miles before being deposited on the ground. Studies show that mercury from the atmosphere can accumulate in areas close to the source.

  Every year, it is estimated that as much as 48 tons of mercury is emitted from coal-fired power plants in the United States. One US Department of Energy (DOE)-Energy Information Bureau's annual energy outlook report shows that coal consumption for power generation will increase to 900 million It is expected to increase from 76 million tons to 1,477 million tons in 2025. However, mercury emission control is not strictly regulated at coal-fired power plants. The main reason is the lack of effective control techniques that are available at reasonable costs, especially the control of elemental mercury.

One technique used to control elemental mercury and mercury oxide is activated carbon injection (ACI). The ACI method includes the steps of injecting activated carbon powder into the flue gas stream and recovering the activated carbon that has adsorbed mercury using a textile fiber or electrostatic precipitator. In general, ACI technology requires a high ratio of carbon to mercury to achieve the desired mercury removal level (> 90%), resulting in increased cost of the adsorbent material. The high ratio of carbon to mercury suggests that ACI does not efficiently utilize the mercury sorption capacity of carbon powder. Furthermore, when only one particle collection system is used, the commercial value of fly ash is sacrificed due to mixing with contaminated activated carbon powder. A system comprising two separate dust collectors and injecting an activated carbon adsorbent between a first dust collector for fly ash and a second dust collector for activated carbon powder or a baghouse may be utilized. A bug house having high collection efficiency may be installed in the power generation facility. However, these measures are expensive and may not be practical, especially in small power plants.

Water-soluble (oxidized) mercury is the main mercury species in the flue gas of bituminous coal with high concentrations of SO ₂ and HCl, and bituminous coal-fired plants are combined with NO _x and / or SO ₂ control technologies It may be possible to remove 90% mercury using the apparatus. Mercury emission control can be realized as a synergistic benefit of particulate emission control. A chelating agent may be added to the cleaning device to suppress mercury re-discharge. Chelating agents increase costs due to the corrosion problems of metal cleaning equipment and the processing of the chelating solution. Elemental mercury is the dominant species of mercury in sub-bituminous or brown coal flue gas, and cleaning equipment is not effective in removing elemental mercury unless additional chemicals are added to the system. However, it is not desirable to add additional potentially hazardous substances to the flue gas system.

  Certain industrial gases, such as synthesis gas and flue gas, include cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic or selenium in addition to mercury Of toxic substances. Like mercury, these toxic substances can exist in the form of elements or in the form of compounds containing elements. It is highly desirable that the presence of one or more of these toxic substances be substantially reduced before the syngas is supplied to industrial and / or residential applications or before the gas is vented to the atmosphere.

There is a real need for adsorbent materials that have higher performance than activated carbon powder alone and are capable of removing mercury and / or other toxic substances from fluids such as flue gas and synthesis gas. It is also desirable that such solvent materials be produced at a reasonable cost and conveniently used.

Embodiments of the present invention relate to adsorbents containing activated carbon, methods for producing them, and methods for using them. The adsorbent can be used to remove toxic substances from a fluid such as a gas stream. For example, the adsorbent can be used to remove elemental mercury or oxidized mercury from coal flue gas.

Embodiments of the invention have one or more of the following advantages. Produces an adsorbent of the present invention comprising activated carbon having a high specific surface area and a large number of active sites capable of adsorbing or promoting adsorption of toxic substances, including arsenic, cadmium, mercury and selenium It can be used effectively for adsorption of substances. The adsorbent according to a specific embodiment of the present invention is effective not only for the adsorption of mercury oxide but also for elemental mercury. Furthermore, the adsorbents of certain embodiments of the present invention are effective in removing mercury from flue gas having similarly high and low HCl concentrations. The adsorbents of certain embodiments of the present invention are also effective in removing mercury from flue gas having a high SO ₃ concentration.

  Additional features and advantages are set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from the description, or in the specification and appended claims. , As well as by implementing the invention as described in the accompanying drawings.

  The foregoing summary and the following detailed description are merely illustrative of the invention and are intended to provide an overview or framework for understanding the nature and characteristics of the invention as recited in the claims. ing.

  The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification.

The mercury removal capacity of an adsorbent test sample, over time, comprising an in situ extruded metal catalyst according to the present invention and an adsorbent comprising impregnated metal but not in situ extruded metal catalyst. Comparison graph. FIG. 6 is a graph showing the inlet mercury concentration (CHg0) and outlet mercury concentration (CHg1) of the sorbent body according to one embodiment of the present invention at various inlet mercury concentrations. FIG. 3 is an SEM image of a portion of a cross-sectional view of an adsorbent according to one embodiment of the present invention that includes an in situ extruded metal catalyst. The SEM image of the part of the cross-sectional view of a comparative adsorption body containing the impregnated metal catalyst after activation.

  Unless otherwise indicated, all numerical values such as weight percentages, dimensions, and values of ingredients for a particular physical property used in the specification and claims are modified by the term “about”. It should be understood that The exact numerical values used in the specification and claims should also be understood as forming additional embodiments of the invention. While efforts are made to ensure the accuracy of the numerical values disclosed in the examples, any measured numerical value may inherently contain some error resulting from the standard deviation found in individual measurement techniques.

  As used herein, the use of the indefinite article “a” or “an” means “at least one” and should be limited to “one” unless expressly indicated otherwise. is not. 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, “% by weight” or “weight percent” or “percentage by weight” of an ingredient refers to the total weight of the composition or article in which the ingredient is included, unless expressly stated otherwise. Is based. As used herein, all percentages are by weight unless otherwise indicated. All ppm for gases are by volume unless otherwise indicated.

 As used herein, the term “sulfur” includes elemental sulfur in all oxidation states including elemental sulfur (0), sulfuric acid (+6), sulfurous acid (+4), and sulfide (−2), among others. Thus, the term sulfur includes sulfur in any oxidation state as elemental sulfur or in a sulfur-containing compound or moiety. The weight percent of sulfur is calculated based on elemental sulfur for any sulfur in other states that are converted to the elemental state for purposes of calculating the total amount of sulfur in the metal.

The term “metal catalyst” includes a metal element in any oxidation state, either as a metal element or in a compound or moiety that contains a metal, which is a toxic substance from a fluid in contact with the adsorbent of the invention ( Removal of cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic, or selenium, or cadmium, mercury, arsenic, or selenium) It exists in a form that promotes. 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 based on the metal element for any metal in other states that are converted to the elemental state for purposes of calculating the total amount of metal catalyst in the metal. Metal elements present in an inert form such as inorganic filler compounds are not considered metal catalysts and do not contribute to the weight percent of the metal catalyst. The amount of sulfur or metal catalyst can be determined using any suitable analytical technique such as mass spectrometry.

 “In-situ extruded” means that at least a portion of the raw material of the relevant substance, such as sulfur and / or metal catalyst, is incorporated into the batch mixed material so that the formed body includes the raw material incorporated therein. , Meaning that related substances such as sulfur and / or metal catalysts are incorporated into the material.

The dispersion of sulfur, metal catalyst or other material across the cross-section of the sorbent body, or extruded batch mixture, or batch mixed material of the present invention includes, but is not limited to, a microprobe, XPS (X-ray photoelectron spectroscopy), and It can be measured by a variety of techniques, including laser ablation combined with mass spectrometry.

Described below is a methodology that characterizes the dispersion of specific materials (eg, sulfur, metal catalysts, etc.) in specific cross-sections of adsorbents or other bodies. This methodology is called “Distribution Characterization Method”.

  If the total cross-section is greater than 500 μm × 500 μm, a target test area with a cross-sectional area of at least 500 μm × 500 μm is selected. For 500 μm × 500 μm or less, the entire cross-section will be a single target test area. The total number of target test areas is p (a positive integer).

であり、
ここでａｅ（ｉ）は区域ｉの有効面積であり、ｎは標的試験領域における試料区域の二乗の総数であり、ここでａｅ（ｉ）≧４０μｍ²である。μｍ²における個々の二乗領域の面積ａｅ（ｉ）は次のように計算される：

ここでａｖ（ｉ）は、二乗領域ｉ内の空間、孔隙または１０μｍ²より大きい空き領域のμｍ²における総面積である。 Each target test area is divided into a plurality of separate 20 μm × 20 μm areas by a grid. Only areas with an effective area of at least 40 μm ² (below) are considered, and those having an effective area of less than 40 μm ² in the data processed below are discarded. Thus, the total effective area (ATE) of the square of the sample area of the target test area is:

And
Where ae (i) is the effective area of area i and n is the total square of the sample area in the target test area, where ae (i) ≧ 40 μm ² . The area ae (i) of the individual square area in μm ² is calculated as follows:

Here av (i) the space in the square area i, a total area of the [mu] m ² of pores or 10 [mu] m ² greater than free space.

ここでＩＮＴ（０．０５×ｎ）は、０．０５×ｎ以上の最小の整数である。本明細書では、演算子「ＩＮＴ（Ｘ）」はＸ以上の最小の整数をもたらす。 Each squared region i has been measured to have an average concentration C (i), expressed in moles of sulfur atoms per unit effective area of sulfur, or moles of other related materials in the case of metal catalysts. Next, all C (i) (i = 1-n) are listed in descending order to form permutations CON (1), CON (2), CON (3),... CON (n), Here, CON (1) is the largest C (i) in all n regions, and CON (n) is the smallest C (i) in all n regions. The 5% arithmetic average concentration of all n regions in the target test region with the highest concentration is CON (max). Therefore:

Here, INT (0.05 × n) is a minimum integer of 0.05 × n or more. As used herein, the operator “INT (X)” results in the smallest integer greater than or equal to X.

標的試験領域の相加平均濃度はＣＯＮ（ａｖ）である。したがって：

すべてのｐ標的試験領域では、すべてのＣＯＮ（ａｖ）（ｋ）（ｋ＝１〜ｐ）は、順列ＣＯＮＡＶ（１）、ＣＯＮＡＶ（２）、ＣＯＮＡＶ（３）、…ＣＯＮＡＶ（ｐ）を形成するために降順で記載され、ここで、ＣＯＮＡＶ（１）は、すべてのｐ標的試験領域の中で最大のＣＯＮ（ａｖ）（ｋ）であり、ＣＯＮＡＶ（ｐ）はすべてのｐ標的試験領域の中で最低のＣＯＮ（ａｖ）（ｐ）である。すべてのｐ標的試験領域の相加平均濃度は、ＣＯＮＡＶ（ａｖ）である。したがって：

物体（body）、または活性炭マトリクス、または材料全体に分散される本発明に従った物体（bodies）または材料の特定の実施の形態では、各標的試験領域におけるそれらの分散が下記の特性を有することが望ましい：ＣＯＮ（ａｖ）／ＣＯＮ（ｍｉｎ）≦３０、およびＣＯＮ（ｍａｘ）／ＣＯＮ（ａｖ）≦３０。特定の他の実施の形態では、ＣＯＮ（ａｖ）／ＣＯＮ（ｍｉｎ）≦２０、およびＣＯＮ（ｍａｘ）／ＣＯＮ（ａｖ）≦２０であることが望ましい。特定の他の実施の形態では、ＣＯＮ（ａｖ）／ＣＯＮ（ｍｉｎ）≦１５、およびＣＯＮ（ｍａｘ）／ＣＯＮ（ａｖ）≦１５であることが望ましい。特定の他の実施の形態では、ＣＯＮ（ａｖ）／ＣＯＮ（ｍｉｎ）≦１０、およびＣＯＮ（ｍａｘ）／ＣＯＮ（ａｖ）≦１０であることが望ましい。特定の他の実施の形態では、ＣＯＮ（ａｖ）／ＣＯＮ（ｍｉｎ）≦５、およびＣＯＮ（ｍａｘ）／ＣＯＮ（ａｖ）≦５であることが望ましい。特定の他の実施の形態では、ＣＯＮ（ａｖ）／ＣＯＮ（ｍｉｎ）≦３、およびＣＯＮ（ｍａｘ）／ＣＯＮ（ａｖ）≦３であることが望ましい。特定の他の実施の形態では、ＣＯＮ（ａｖ）／ＣＯＮ（ｍｉｎ）≦２、およびＣＯＮ（ｍａｘ）／ＣＯＮ（ａｖ）≦２であることが望ましい。 The 5% arithmetic average concentration of all n regions in the target test region with the lowest concentration is CON (min). Therefore:

The arithmetic mean concentration of the target test area is CON (av). Therefore:

In all p target test areas, all CON (av) (k) (k = 1-p) form the permutations CONAV (1), CONAV (2), CONAV (3),... CONAV (p) Are described in descending order, where CONAV (1) is the largest CON (av) (k) of all p-target test areas and CONAV (p) is And the lowest CON (av) (p). The arithmetic mean concentration of all p-target test areas is CONAV (av). Therefore:

In a particular embodiment of the body, or activated carbon matrix, or body or material according to the invention dispersed throughout the material, their dispersion in each target test area has the following properties: Are preferred: CON (av) / CON (min) ≦ 30 and CON (max) / CON (av) ≦ 30. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 20 and CON (max) / CON (av) ≦ 20. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 15 and CON (max) / CON (av) ≦ 15. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 10 and CON (max) / CON (av) ≦ 10. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 5 and CON (max) / CON (av) ≦ 5. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 3 and CON (max) / CON (av) ≦ 3. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 2 and CON (max) / CON (av) ≦ 2.

  For certain materials or components to be “homogeneously dispersed” to have “homogeneous dispersion” in an object or material according to the application of the present invention, their dispersion according to the distribution characteristics method satisfies: For all CON (m), 0.1 n ≦ m ≦ 0.9 n in the target test area: 0.5 ≦ CON (m) / CON (av) ≦ 2.

In certain embodiments, it is desirable that 0.6 ≦ CON (m) / CON (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CON (m) / CON (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CON (m) / CON (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CON (m) / CON (av) ≦ 1.1. In a particular embodiment, for all CON (m), where 0.05n ≦ m ≦ 0.95n: 0.5 ≦ CON (m) / CON (av) ≦ 2; Then, 0.6 ≦ CON (m) / CON (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CON (m) / CON (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CON (m) / CON (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CON (m) / CON (av) ≦ 1.1. In certain embodiments of the invention ( adsorbents , extrusion blends, etc.) and materials of the invention, in addition to any one of the above properties in this paragraph for each distinct target test area, all p targets The dispersion of relevant materials (eg, sulfur, metal catalyst, etc.) for the test area has the following properties: for all CONAV (k), where 0.1p ≦ k ≦ 0.9p: 0.5 ≦ CONAV (k) / CONAV (av) ≦ 2; in certain embodiments, 0.6 ≦ CONAV (k) / CONAV (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CONAV (k) / CONAV (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CONAV (k) / CONAV (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CONAV (k) / CONAV (av) ≦ 1.1. In certain other embodiments, it is desirable that 0.95 ≦ CONAV (k) / CONAV (av) ≦ 1.05. In a particular embodiment, for all CONAV (k) where 0.5p ≦ k ≦ 0.95p: 0.5 ≦ CONAV (k) / CONAV (av) ≦ 2; 0.6 ≦ CONAV (k) / CONAV (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CONAV (k) / CONAV (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CONAV (k) / CONAV (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CONAV (k) / CONAV (av) ≦ 1.1. In certain other embodiments, it is desirable that 0.95 ≦ CONAV (k) / CONAV (av) ≦ 1.05.

One aspect of the present invention is:
An activated carbon matrix;
Sulfur in any oxidation state as elemental sulfur or in a compound or moiety containing sulfur; and
A metal catalyst in any oxidation state as a metal element or in a compound or moiety containing a metal;
Including
The metal catalyst is dispersed throughout the activated carbon matrix;
It is an adsorbent .

In this embodiment and any other embodiment of the sorbent body of the present invention, sulfur can be dispersed throughout the activated carbon matrix. In some embodiments, the metal catalyst and / or sulfur is substantially homogeneously dispersed throughout the activated carbon matrix. In some embodiments, at least some of the metal catalyst is chemically bonded to at least some of the sulfur. Thus, a single compound comprising a metal catalyst and sulfur, such as a metal sulfide, can provide both sulfur and metal catalyst in the adsorbent . The phrase “at least a portion” of sulfur or metal catalyst refers to the content of some or all of the sulfur or metal catalyst in the adsorbent . In some further embodiments, at least some sulfur is chemically bonded to at least some carbon of the activated carbon matrix.

In this and other embodiments of the sorbent body of the present invention, at least a portion of sulfur, metal catalyst, or both sulfur and metal catalyst is cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt , Vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic, or selenium. For example, at least a portion of the sulfur can be in a state that has the ability to chemically bond with mercury.

The adsorbents of this and other embodiments described herein include, for example, coal combustion or waste incineration produced during the coal gasification process, or flue gas streams resulting from synthesis gas, etc. Can be adapted to remove mercury and other toxic substances from the fluid stream. Such gas streams can include various amounts of mercury and / or cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and selenium. Of toxic substances. Other toxic substances, such as mercury, can be contained in such gas streams in various proportions in elemental or oxidized states, depending on the raw material (eg bituminous coal, subbituminous coal, municipal waste, and medical waste) and working conditions. Can exist. In some embodiments, the sorbent body includes a metal catalyst adapted to facilitate the removal of arsenic, cadmium, mercury and / or selenium from the fluid stream to be treated.

Through a combination of physical and chemical adsorption, the sorbent body of the present invention is believed to have the ability to bind and trap mercury and other toxic substances in both the elemental and oxidation states. The adsorbents and materials of certain embodiments of the present invention are particularly effective in removing elemental mercury in flue gas streams. This is particularly advantageous compared to certain other techniques that are usually less effective at removing elemental mercury.

The adsorbent of the present invention can take various shapes. For example, the adsorbent can be a powder, pellets, and / or an extruded monolith. The adsorbent of the present invention can be incorporated into a fixed adsorbent bed through which the fluid stream to be treated will flow. In certain embodiments, particularly when used to treat coal flue gas at power plants, or synthesis gas produced in the process of coal gasification, any fixed bed through which the gas stream passes has a low pressure drop. It is highly desirable to have For this purpose, it is desirable that the adsorption pellets filled in the fixed bed allow a sufficient gas flow path.

According to a particular embodiment, the adsorbent is in the form of a monolith. According to a particular embodiment, the adsorbent is in the form of a monolithic honeycomb having a plurality of channels through which gas or liquid can pass.

In certain embodiments, it is particularly advantageous to be in the form of an extruded monolith honeycomb having a plurality of channels. In order to achieve varying degrees of pressure loss in use, the cell density of the honeycomb can be adjusted during the extrusion process. The cell density of the honeycomb can be in the range of 25 to 500 cell-inch- ² (3.88 to 77.5 cell · cm ⁻² ) in certain embodiments, and in certain other embodiments. 50-200 cell-inch- ² (7.75-31.0 cell-cm ^-2 ), and in still other specific embodiments, 50-100 cell-inch- ² (7.75-15.5 cell- cm ⁻² ). In certain embodiments, the cell wall thickness ranges from 2.54 × 10 ⁻³ cm to 1.27 × 10 ⁻¹ cm (1 mil to 50 mils), for example, 2.54 × 10 ^{− 2} cm to 7.62 × 10 ⁻² cm (10 mil to 30 mil). To allow more intimate contact between the gas stream and the adsorption material, in certain embodiments, a portion of the channel is blocked at one end of the adsorbent, a part of the channels of the adsorbent It is desirable to be plugged at the other end. In certain embodiments, at each end of the adsorbent , it is desirable that the blocked and / or unblocked channels form a checkerboard pattern. In certain embodiments, a channel is immediately adjacent if it is blocked at one end (referred to as the “reference end”) but not at the opposite end of the adsorbent. At least the majority of the channels (preferably all of the other specific embodiments) are at the other end of the adsorbent (sharing at least one wall with the channel of concern) It is desirable that it is plugged but not plugged at the reference end. A large number of honeycombs can be laminated in various ways with the aim of forming actual adsorption beds with different dimensions, durations of use, etc. to meet the demands of different usage conditions.

As used herein, “activated carbon matrix” means a network formed by interconnected carbon atoms and / or particles. In some embodiments, the activated carbon matrix in the sorbent body of the present invention is in the form of an uninterrupted and continuous object. As seen in typical activated carbon materials, the matrix includes a wall structure that defines a plurality of pores. The activated carbon matrix, along with sulfur and metal catalysts, can provide an adsorbent skeletal structure. Furthermore, the large cumulative area of pores in the activated carbon matrix provides multiple locations where mercury adsorption can occur directly or where sulfur and metal catalysts can be dispersed, which further promotes mercury adsorption. It should be noted that the pores defined by the activated carbon matrix can be different from those actually present in the adsorbent . For example, some pores defined by the activated carbon matrix can be filled with metal catalysts, sulfur, inorganic fillers, and combinations and mixtures thereof.

In certain embodiments, the sorbent body includes 50% to 97% by weight activated carbon, and in certain embodiments, 60% to 97%, or 85% to 97% activated carbon. In other embodiments, the sorbent body comprises at least 50 wt% activated carbon, such as at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 97 wt%. Contains weight percent activated carbon. Higher concentrations of activated carbon are typically higher when made according to the methods described herein if the same level of carbonization and activation is used during the process of making the adsorbent. It can lead to porosity.

  The pores defined by the activated carbon matrix can be divided into two categories: nanoscale pores having a diameter of 10 nm or less, and microscale pores having a diameter greater than 10 nm. According to certain embodiments, the activated carbon matrix defines a plurality of nanoscale pores. The metal catalyst or sulfur can be present, for example, on at least some of the wall surfaces of the nanoscale pores. According to certain embodiments, the activated carbon matrix further defines a plurality of microscale pores.

Pore size and its dispersion in the adsorbent can be determined by using available techniques available in the art, such as for example, nitrogen adsorption. Both nanoscale and microscale pore surfaces provide the overall high specific surface area of the sorbent body of the present invention. In certain embodiments, the nanoscale pore wall surface comprises a specific surface area of at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the sorbent body.

The adsorbent of the present invention can have a large specific surface area. In certain embodiments of the present invention, the sorbent ^{body, 50~2000m 2 · g -1, 200~2000m} 2 · g -1, 400~1500m 2 · g -1, 100~1800m 2 · g -1, 200~1500m ² · g ^-1, or having a specific surface area in the range of 300~1200m ² · g ^-1. The higher specific surface area of the adsorbent can provide more active sites in the material for adsorbing toxic substances. However, if the specific surface area of the adsorbent is very high, for example higher than 2000 m ² · g ⁻¹ , the adsorbent becomes very porous and the mechanical integrity of the adsorbent can be compromised. This may not be desirable for certain applications where the strength of the adsorbent requires specific threshold requirements.

The metal catalyst included in the embodiment of the present invention includes cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium from a fluid in contact with the adsorbent. The removal of one or more toxic substances such as arsenic, selenium, or selenium, where any of the toxic substances can be in any oxidation state, and the elemental form or the element It can be a compound containing. Ability to facilitate removal of toxic substances or compounds, including mercury, arsenic, cadmium, or selenium, derived from a fluid, such as a fluid stream to be treated upon contact (herein referred to as “reduction of toxic substances or compounds” Any such metal catalyst having the term "" can be included in the adsorbent of the present invention. In this regard, the terms “removal” and “reduction” are used interchangeably herein. Furthermore, these terms are also understood to extend to reducing the presence of toxic substances by a matter of degree in the fluid, i.e. by a certain proportion, and are not limited to complete removal or reduction of toxic substances. Absent. In some embodiments, the metal catalyst may function in one or more of the following ways to facilitate removal (or reduction) of toxic substances from the fluid in contact with the adsorbent : (i) toxic substances Temporary or permanent chemisorption of (e.g., via covalent and / or ionic bonding); (ii) temporary or permanent physical adsorption of toxic substances; (iii) other toxic substances other than adsorbents ; (Iv) conversion of toxic substances from one to another by catalyzing the reaction of toxic substances in the ambient atmosphere; (v) already by other components of the adsorbent Capture of adsorbed toxic substances; and (vi) facilitating migration of toxic substances to active adsorption sites.

According to particular embodiments of the sorbent body of the present invention, the metal catalyst may be provided in a form selected from: (i) alkali and alkaline earth metal halides and oxides; (ii) noble metals and (Iii) oxides, sulfides, and salts of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver, tungsten, and lanthanoids; and (iv) (i), Combinations and mixtures of two or more of (ii) and (iii).

For example, the metal catalyst may be provided in a form selected from: (i) oxides, sulfides and manganese salts; (ii) oxides, sulfides and iron salts; (iii) (i) and A combination of KI; (iv) a combination of (ii) and KI; and (v) a mixture and combination of any two or more of (i), (ii), (iii) and (iv). In a particular embodiment of the invention, the adsorbent comprises an alkaline earth metal hydroxide as a metal to facilitate the removal of toxic substances such as Ca (OH) ₂ .

Noble metals (Ru, Th, Pd, Ag, Re, Os, Ir, Pt and Au) and transition metals and their compounds are typical metal catalysts. Further non-limiting metal catalysts include alkali and alkaline earth halides, hydroxides or oxides; and oxides, sulfides, and vanadium, chromium, manganese, iron, cobalt, nickel, copper, Includes zinc, niobium, molybdenum, silver, tungsten, and lanthanoid salts. The metal catalyst can be present in any valence. For example, if iron is present, it may be present at a valence of +3, +2 or 0, or as a mixture of different valences, and may be metallic iron (0), FeO, Fe ₂ O ₃ , Fe ₃ O ₈ , FeS, FeCl ₂ , FeCl ₃ , FeSO _{4 and the} like. In another example, if manganese is present, it can be present at a valence of +4, +2 or 0, or as a mixture of different valences, and can be metallic manganese (0), MnO, MnO ₂ , MnS, MnCl ₂ , MnCl ₄ , MnSO ₄ , and the like. In some embodiments, the metal catalyst is not in the form of an oxide. In other embodiments, the adsorbent comprises at least one metal catalyst that is not in the form of an oxide.

In certain embodiments of the sorbent body of the present invention, the metal catalyst is in a form selected from: alkali halides; and manganese and iron oxides, sulfides, and salts. In a particular embodiment of the sorbent body of the present invention, the metal catalyst is in a form selected from: KI and manganese oxides, sulfides, and salt combinations; KI and iron oxides, sulfides Or combinations of KI and manganese and iron oxides, sulfides, and salts. These combinations have been found to be particularly effective in removing mercury, particularly elemental mercury from gas streams.

According to a particular embodiment of the invention, the adsorbent comprises an alkaline earth metal hydroxide as a metal for promoting the removal of toxic substances such as Ca (OH) ₂ . Experiments have shown that Ca (OH) ₂ is particularly effective in removing arsenic, cadmium, and selenium from gas streams.

In some embodiments of the invention, the metal catalyst is an alkali metal such as lithium, sodium or potassium. In other embodiments, the metal catalyst is an alkaline earth metal such as magnesium, calcium or barium. In other embodiments, the metal catalyst is a transition metal such as palladium, platinum, silver, gold, manganese, or iron. In other embodiments, the metal catalyst is a rare earth metal such as cerium. In some embodiments, the metal catalyst is present in elemental form. In other embodiments, the metal catalyst is a metal sulfide. In other embodiments, the metal catalyst is a transition metal sulfide or oxide. In yet another embodiment, the adsorbent comprises at least one catalyst other than an alkali metal, alkaline earth metal, or transition metal. In other embodiments, the adsorbent comprises at least one catalyst other than sodium, other than potassium, other than magnesium, other than calcium, other than aluminum, other than titanium, other than zirconium, other than chromium, other than magnesium, other than iron, and / or zinc. Includes types. In other embodiments, the adsorbent comprises at least one metal catalyst other than aluminum, vanadium, iron, cobalt, nickel, copper, or zinc, in elemental form or as a sulfate.

The amount of the metal catalyst present in adsorber specific metal catalyst used, and applications that use adsorber and the adsorbent can be selected depending on the removal ability and efficiency of toxic substances desired. In certain embodiments of the sorbent body of the present invention, the amount of metal catalyst ranges from 1% to 20% by weight, in certain other embodiments from 2% to 18%, in certain other implementations. The form ranges from 5% to 15% and in certain other embodiments from 5% to 10%. In further embodiments, the adsorbent is 1 wt% to 25 wt% metal catalyst (1% -20%, 1% -15%, 3% -10%, or 3-5% in certain embodiments). including.

In a specific embodiment that states that a metal catalyst is dispersed in an activated carbon matrix, if there is only one type of metal catalyst in the adsorbent , the metal catalyst is dispersed throughout the activated carbon matrix. When multiple metal catalysts are present, in these embodiments, at least one of the catalysts is dispersed throughout the activated carbon matrix. “Dispersed throughout the activated carbon matrix” means that the specific materials involved (metal catalyst, sulfur, etc.) are not only present on the outer surface of the adsorbent or cell wall, but also deep inside the adsorbent. Means that. Thus, the presence of a particular metal catalyst may be, for example: (i) a nanoscale pore wall surface defined by an activated carbon matrix; (ii) a microscale pore wall surface defined by an activated carbon matrix; (iii) Embedded in the wall structure of the activated carbon matrix; (iv) partially embedded in the wall structure of the activated carbon matrix; (v) partially filled and / or blocked with some pores defined by the activated carbon matrix. And (vi) completely filling and / or blocking some pores defined by the activated carbon matrix. In the (iii), (iv), (v) and (vi) states, the metal catalyst and / or other components dispersed in the activated carbon matrix actually forms part of the pore wall structure of the adsorbent. . In certain embodiments, there are a plurality of metal catalysts, all of which are dispersed throughout the activated carbon matrix. However, it is not necessary for all metal catalysts to be dispersed throughout the activated carbon matrix. Thus, in certain embodiments, the plurality of metal catalysts are at least one of which is dispersed throughout the activated carbon matrix, and at least one of them is primarily comprised of the outer surface area and / or cell walls of the adsorbent. It exists in a substantially dispersed state on the surface and / or in the lamina just below the outer surface area and / or cell wall surface. In certain embodiments, at least a portion of the metal catalyst can be chemically combined with other components of the sorbent body, such as carbon or sulfur. In certain other embodiments, at least a portion of the metal catalyst can be physically associated with the activated carbon matrix or other components. In still other specific embodiments, at least a portion of the metal catalyst is present in the adsorbent in the form of particles having a nanoscale or microscale size.

The dispersion of the metal catalyst in the adsorbent or other object or material according to the present invention can be measured and characterized by the distribution characteristic method described above. In a particular embodiment of the sorbent body of the present invention, the dispersion of the metal catalyst has the following characteristics: In each target test area: CON (av) / CON (min) ≦ 30, and CON (max) / CON (Av) ≦ 30. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 20 and CON (max) / CON (av) ≦ 20. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 15 and CON (max) / CON (av) ≦ 15. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 10 and CON (max) / CON (av) ≦ 10. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 5 and CON (max) / CON (av) ≦ 5. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 3 and CON (max) / CON (av) ≦ 3. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 2 and CON (max) / CON (av) ≦ 2.

In certain embodiments of the sorbent body of the present invention, at least one metal catalyst is homogeneously dispersed throughout the activated carbon matrix according to the distribution characteristics method described above. Therefore: In each target test area, for all CON (m) where 0.1n ≦ m ≦ 0.9n: 0.5 ≦ CON (m) / CON (av) ≦ 2.

In certain embodiments, it is desirable that 0.6 ≦ CON (m) / CON (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CON (m) / CON (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CON (m) / CON (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CON (m) / CON (av) ≦ 1.1. In a particular embodiment, for all CON (m) where 0.05n ≦ m ≦ 0.95n: 0.5 ≦ CON (m) / CON (av) ≦ 2; in a particular embodiment 0.6 ≦ CON (m) / CON (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CON (m) / CON (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CON (m) / CON (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CON (m) / CON (av) ≦ 1.1. In certain embodiments of the objects ( adsorbents , extrusion blends, etc.) and materials of the present invention, all in addition to any one of the properties previously described in this section for each distinct target test area The dispersion of relevant materials (eg, sulfur, metal catalysts, etc.) for the p target test region of the following has the following characteristics: For all CONAV (k) where 0.1p ≦ k ≦ 0.9p: 0.5 ≦ CONAV (k) / CONAV (av) ≦ 2; in certain embodiments, 0.6 ≦ CONAV (k) / CONAV (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CONAV (k) / CONAV (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CONAV (k) / CONAV (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CONAV (k) / CONAV (av) ≦ 1.1. In certain other embodiments, it is desirable that 0.95 ≦ CONAV (k) / CONAV (av) ≦ 1.05. In a particular embodiment, for all CONAV (k) where 0.5p ≦ k ≦ 0.95p: 0.5 ≦ CONAV (k) / CONAV (av) ≦ 2; 0.6 ≦ CONAV (k) / CONAV (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CONAV (k) / CONAV (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CONAV (k) / CONAV (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CONAV (k) / CONAV (av) ≦ 1.1. In certain other embodiments, it is desirable that 0.95 ≦ CONAV (k) / CONAV (av) ≦ 1.05.

  In a particular embodiment of the invention, the metal catalyst is present on the majority of the microscale pore wall surface. In certain other embodiments of the invention, the metal catalyst is present in at least 75%, at least 90% or at least 95% of the wall surface of the microscale pores.

In certain embodiments of the invention, the metal catalyst is present in at least 20%, at least 40%, at least 50%, at least 75%, or at least 85% of the nanoscale pore wall surface. In certain embodiments, the majority of the specific surface area of the sorbent body is provided by the nanoscale pore wall surface. In these embodiments, it is desirable for the metal catalyst to be dispersed at a high rate on the wall surface of the nanoscale pores.

The adsorbent of the present invention contains sulfur. The amount of sulfur present in adsorber specific metal catalyst used, applications where the adsorbent is used, and, of the adsorbent, can be selected according to the removing capacity and efficiency of the desired toxic substances.

In some embodiments, the sorbent body comprises 1% to 20% by weight sulfur (in certain embodiments, 1% to 15%, 3% to 8%, 2% to 10%,. 1-5%, or 2-5%). Sulfur may be present in the form of elemental sulfur (valence 0), sulfide (e.g. valence -2), sulfurous acid (e.g. valence +4), sulfuric acid (e.g. valence +6). In some embodiments, sulfur is not present as sulfate or sulfate is not the only source of sulfur in the adsorbent . Desirably, at least some of the sulfur is present at a valence capable of chemically combining with a toxic substance to be removed from the fluid stream, such as mercury. For this purpose, it is desirable that at least part of the sulfur be present with a valence of -2 and / or 0. At least a portion of the sulfur can be chemically or physically bound to the wall surface of the activated carbon matrix. At least a portion of the sulfur can be chemically or physically bound to the metal catalyst, as described above, for example in the form of sulfides (FeS, MnS, Mo ₂ S ₃ , CuS, etc.).

In some embodiments, at least some sulfur has a valence of zero. For example, at least 10% of the sulfur on the surface of the pore walls of the activated carbon matrix is substantially zero valence as measured by XPS. In other embodiments, at least some of the sulfur is non-zero. In some embodiments, the sorbent body includes some non-valent sulfur and some non-zero sulfur. In some embodiments, the sorbent body includes elemental sulfur as well as sulfur present in the form of sulfur-containing compounds, such as metal sulfides.

In certain embodiments, it is desirable that at least 40 mole percent, at least 50 mole percent, at least 60 mole percent, or at least 70 mole percent sulfur in the sorbent body have a valence of zero. According to certain embodiments, at least 10%, at least 20%, at least 30%, at least 40%, at least 50% or at least 60% of the sulfur on the surface of the pore walls is substantially as measured by XPS. The valence is 0.

Experiments have demonstrated that activated carbon, sulfur and metal catalyst adsorbents can be effective in removing arsenic, cadmium, and selenium from gas streams in addition to mercury. Experiments have demonstrated that adsorbents containing elemental sulfur tend to have higher mercury removal capabilities than those that do not contain elemental sulfur but have substantially the same sulfur concentration.

In certain embodiments, sulfur is dispersed throughout the activated carbon matrix. “Dispersed throughout the activated carbon matrix” means that sulfur is not only present on the outer surface of the adsorbent or cell wall, but also deep inside the adsorbent . Thus, the presence of sulfur is, for example: (i) nanoscale pore wall surface; (ii) microscale pore wall surface; (iii) buried in the wall structure of the activated carbon matrix; and (iv) the activated carbon matrix wall. It can be partially embedded in the structure. In the (iii) and (iv) states, sulfur actually forms part of the pore wall structure of the adsorbent . Thus, in certain embodiments, some sulfur may be chemically coupled (covalent and / or ionic) with other components of the adsorbent, such as carbon or metal catalysts. In certain other embodiments, some sulfur may be physically combined with the activated carbon matrix or other components. In still other specific embodiments, some sulfur is present in the adsorbent in the form of particles having a nanoscale or microscale size.

The dispersion of sulfur in the adsorbent or other object or material according to the present invention can be measured and characterized by the distribution characteristic method described above.

  In certain embodiments, the dispersion of sulfur in any target test region has the following properties: CON (max) / CON (min) ≧ 100. In certain other embodiments: CON (max) / CON (min) ≧ 200. In certain other embodiments: CON (max) / CON (min) ≧ 300. In certain other embodiments: CON (max) / CON (min) ≧ 400. In certain other embodiments: CON (max) / CON (min) ≧ 500. In certain other embodiments: CON (max) / CON (min) ≧ 1000. In certain other embodiments: CON (max) / CON (av) ≧ 50. In certain other embodiments: CON (max) / CON (av) ≧ 100. In certain other embodiments: CON (max) / CON (av) ≧ 200. In certain other embodiments: CON (max) / CON (av) ≧ 300. In certain other embodiments: CON (max) / CON (av) ≧ 400. In certain other embodiments: CON (max) / CON (av) ≧ 500. In certain other embodiments: CON (max) / CON (av) ≧ 1000.

In certain embodiments, for sulfur dispersed in the sorbent body, its dispersion in all p target test regions has the following properties: CONAV (1) / CONAV (n) ≧ 2. In certain other embodiments: CONAV (1) / CONAV (n) ≧ 5. In certain other embodiments: CONAV (1) / CONAV (n) ≧ 8. In certain other embodiments: CONAV (1) / CONAV (n) ≧ 1.5. In certain other embodiments: CONAV (1) / CONAV (av) ≧ 2. In certain other embodiments: CONAV (1) / CONAV (av) ≧ 3. In certain other embodiments: CONAV (1) / CONAV (av) ≧ 4. In certain other embodiments: CONAV (1) / CONAV (av) ≧ 5. In certain other embodiments: CONAV (1) / CONAV (av) ≧ 8. In certain other embodiments: CONAV (1) / CONAV (av) ≧ 10.

In certain other embodiments, with respect to sulfur dispersed in the adsorbent , in each target test region, the dispersion has the following properties: CON (av) / CON (min) ≦ 30. In certain other embodiments: CON (av) / CON (min) ≦ 20. In certain other embodiments: CON (av) / CON (min) ≦ 15. In certain other embodiments: CON (av) / CON (min) ≦ 10. In certain other embodiments: CON (av) / CON (min) ≦ 5. In certain other embodiments: CON (av) / CON (min) ≦ 3. In certain other embodiments: CON (av) / CON (min) ≦ 2. In certain other embodiments: CON (max) / CON (av) ≦ 30. In certain other embodiments: CON (max) / CON (av) ≦ 20. In certain other embodiments: CON (max) / CON (av) ≦ 15. In certain other embodiments: CON (max) / CON (av) ≦ 10. In certain other embodiments: CON (max) / CON (av) ≦ 5. In certain other embodiments: CON (max) / CON (av) ≦ 3. In certain other embodiments: CON (max) / CON (av) ≦ 2.

In particular embodiments of the sorbent body of the present invention, sulfur dispersion has the following properties: CON (av) / CON (min) ≦ 30 and CON (max) / CON (av) in each target test area. ) ≦ 30. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 20 and CON (max) / CON (av) ≦ 20. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 15 and CON (max) / CON (av) ≦ 15. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 10 and CON (max) / CON (av) ≦ 10. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 5 and CON (max) / CON (av) ≦ 5. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 3 and CON (max) / CON (av) ≦ 3. In certain other embodiments, it is desirable that CON (av) / CON (min) ≦ 2 and CON (max) / CON (av) ≦ 2.

In certain embodiments of the sorbent body of the present invention, sulfur is homogeneously dispersed throughout the activated carbon matrix according to the distribution characteristics method described above. Therefore: In each target test area, for all CON (m) where 0.1n ≦ m ≦ 0.9n: 0.5 ≦ CON (m) / CON (av) ≦ 2.

In certain embodiments, it is desirable that 0.6 ≦ CON (m) / CON (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CON (m) / CON (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CON (m) / CON (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CON (m) / CON (av) ≦ 1.1. In a particular embodiment, for all CON (m), where 0.05n ≦ m ≦ 0.95n: 0.5 ≦ CON (m) / CON (av) ≦ 2; Then, 0.6 ≦ CON (m) / CON (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CON (m) / CON (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CON (m) / CON (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CON (m) / CON (av) ≦ 1.1. In certain embodiments of the objects ( adsorbents , extrusion blends, etc.) and materials of the present invention, each for a separate target test area, in addition to any one of the above-mentioned properties in this section, all The dispersion of relevant materials (eg, sulfur, metal catalysts, etc.) for the p target test area has the following properties: For all CONAV (k) where 0.1p ≦ k ≦ 0.9p: 0.5 ≦ CONAV (k) / CONAV (av) ≦ 2; in a specific embodiment, 0.6 ≦ CONAV (k) / CONAV (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CONAV (k) / CONAV (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CONAV (k) / CONAV (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CONAV (k) / CONAV (av) ≦ 1.1. In certain other embodiments, it is desirable that 0.95 ≦ CONAV (k) / CONAV (av) ≦ 1.05. In a particular embodiment, for all CONAV (k) where 0.5p ≦ k ≦ 0.95p: 0.5 ≦ CONAV (k) / CONAV (av) ≦ 2; 0.6 ≦ CONAV (k) / CONAV (av) ≦ 1.7. In certain other embodiments, it is desirable that 0.7 ≦ CONAV (k) / CONAV (av) ≦ 1.4. In certain other embodiments, it is desirable that 0.8 ≦ CONAV (k) / CONAV (av) ≦ 1.2. In certain other embodiments, it is desirable that 0.9 ≦ CONAV (k) / CONAV (av) ≦ 1.1. In certain other embodiments, it is desirable that 0.95 ≦ CONAV (k) / CONAV (av) ≦ 1.05.

  In certain embodiments, sulfur is present in the majority of the microscale pore wall surface. In certain other embodiments, sulfur is present in at least 75%, at least 90%, or at least 95% of the wall surface of the microscale pores.

In certain embodiments, sulfur is present in at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 85% of the nanoscale pore wall surface. In certain embodiments, the majority of the specific surface area of the sorbent body is provided by the nanoscale pore wall surface. In these embodiments, it is desirable to have a high percentage of sulfur (such as at least 40%, at least 50%, or at least 60%) dispersed on the wall surface of the nanoscale pores.

The adsorbent can further comprise an inorganic filler material. In contrast to metal catalysts, any metal element in the inorganic filler material is chemically and physically inert. Thus, in one or more of the following methods for facilitating the removal of toxic substances from the fluid in contact with the adsorbent of the present invention, the metallic elements contained in the inorganic filler are not functioning: (i) Temporary or permanent chemical adsorption of toxic substances (eg, via covalent and / or ionic bonds); (ii) temporary or permanent physical adsorption of toxic substances; (iii) other adsorbents A catalyst for reaction / adsorption of toxic substances using the components of: (iv) a catalyst for reaction using ambient atmosphere to convert toxic substances from one to another; (v) by other components of the adsorbent Capture of already adsorbed toxic substances; and (vi) facilitating the transfer of toxic substances to active adsorption sites.

Inorganic fillers are included, inter alia, for the purpose of reducing costs and improving the physical properties of the adsorbent (thermal expansion coefficient; fracture stress, etc.); or chemical properties (water resistance; Such an inorganic filler can be an oxide glass, an oxide ceramic, or a specific heat resistant material. Non-limiting examples of inorganic fillers include silica; alumina; zircon; zirconia; mullite; cordierite; In certain embodiments, the inorganic filler is itself porous. The high porosity of the inorganic filler can improve the mechanical strength of the adsorbent without sacrificing the specific surface area excessively. The inorganic filler can be dispersed throughout the adsorbent . The inorganic filler can be present in the form of very small particles dispersed in the adsorbent . Depending on the application of the sorbent body and other elements, in certain embodiments, the sorbent body can include, for example, up to 50% by weight inorganic filler, and in certain other embodiments, up to 40%. In certain other embodiments, up to 30%, in certain other embodiments up to 20%, in certain other embodiments up to 10% inorganic filler may be included.

For the purpose of providing high specific surface area of the sorbent body, if that contains inorganic filler, the adsorbent, and a the inorganic filler is porous in adsorbent height of the specific surface area of the adsorbent It is desirable to contribute to a certain extent. It is usually difficult or expensive to include in the adsorbent an inorganic filler having a specific surface area comparable to that of activated carbon. Thus, in addition to the typical mechanical reinforcement that such inorganic fillers would bring to the final adsorber , the overall specific surface area of the adsorbent also tends to be impaired. This can be highly undesirable in some cases. The large surface area of the adsorbent is usually a more active site for toxic substance adsorption (carbon sites capable of adsorbing toxic substances, sulfur capable of promoting or inducing toxic substances, and Means a metal catalyst that promotes the adsorption of toxic substances. Furthermore, it considered three categories near the active adsorption sites in the adsorbent promotes all adsorption capacity.

In addition to the total average distance between and within these three categories of active sites, the incorporation of large amounts of inorganic filler dilutes the metal catalyst and sulfur in the carbon matrix. Thus, in some embodiments, the sorbent body has a relatively low proportion of inorganic filler (the remainder of the sorbent body is carbon, sulfur and metal catalysts). In certain embodiments, the adsorbent is less than 40%, less than 30%, less than 20%, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5% by weight, Contains less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% inorganic filler. In one embodiment, the adsorber does not include an inorganic filler. Adsorbents containing smaller amounts of inorganic filler can lead to a more homogeneous distribution of mercury capture across the wall cross section of the activated carbon matrix. Thus, in certain embodiments, the adsorbent has a total amount of activated carbon, sulfur and metal catalyst of at least 90% by weight (in certain embodiments, at least 91%, at least 92%, at least 93%, at least 94% , At least 95%, at least 96%, at least 97%, or at least 98%).

In a further embodiment of the invention, the adsorbent is
Activated carbon,
Sulfur in any oxidation state as elemental sulfur or in a compound or moiety containing sulfur; and
A metal catalyst in any oxidation state as a metal element or in a compound or moiety containing a metal;
Where, where
At least a portion of the metal catalyst is chemically bonded to at least a portion of the sulfur.

In another embodiment of the sorbent body disclosed herein, at least a portion of the sulfur can be chemically bonded to at least a portion of the carbon of the activated carbon matrix. Sulfur and / or metal catalysts may be dispersed throughout the activated carbon matrix in some embodiments. In other embodiments, the sulfur and / or metal catalyst is not dispersed throughout the activated carbon matrix. The sorbent body of this embodiment and any other embodiment can include a metal sulfide such as manganese sulfide. The adsorbent of this embodiment also includes any one or more other features mentioned for any other adsorbent of the present invention, including the features of activated carbon, sulfur, and metal catalysts described above. sell.

ここでＣ₀は吸着床の直前の燃焼排ガス流れにおけるμｇ・ｍ^-3での総水銀濃度であり、Ｃ₁は吸着床の直後のμｇ・ｍ^-3での総水銀濃度である。初期の水銀除去効率は、新鮮な試験吸着材料を充填後最初の１時間の平均水銀除去効率として定義される。典型的には、固定吸着床の水銀除去効率は、吸着床が徐々に水銀で満たされるため、時間と共に低下する。水銀除去能力は、上記試験条件下で、初期の水銀除去効率が９０％に低下するまで、吸着体材料の単位質量あたりの吸着床によって捕捉される水銀の総量として定義される。水銀除去能力は、典型的には吸着材料（ｍｇ・ｇ^-1）のグラムあたりの捕捉される水銀のｍｇで表される。 Embodiments of the sorbent body of the present invention are derived from fluids such as synthesis gas streams and flue gas streams, such as cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, It is believed that toxic substances such as antimony, silver, thallium, arsenic and selenium can be adsorbed and removed. Adsorbents have been found to be particularly effective in removing mercury from flue gas streams. The removal capacity of adsorbent material for a particular toxic substance, such as mercury, is typically characterized by two parameters: initial removal efficiency and long-term removal ability. For mercury, the following procedure is used to characterize initial mercury removal efficiency and long-term mercury removal capacity:
The adsorbent to be tested is packed into a fixed bed through which a 160 ° C. reference flue gas having a specific composition passes at a space velocity of 7500 hours ⁻¹ . The mercury concentration in the gas stream is measured before and after the adsorption bed. At any point in time, the instantaneous mercury removal efficiency (Eff (Hg)) is calculated as follows:

Here, C ₀ is the total mercury concentration at μg · m ⁻³ in the combustion exhaust gas flow immediately before the adsorption bed, and C ₁ is the total mercury concentration at μg · m ⁻³ immediately after the adsorption bed. Initial mercury removal efficiency is defined as the average mercury removal efficiency for the first hour after filling with fresh test adsorbent material. Typically, the mercury removal efficiency of a fixed adsorbent bed decreases with time because the adsorbent bed is gradually filled with mercury. Mercury removal capacity at the test conditions described above, to the initial mercury removal efficiency is reduced to 90%, it is defined as the total amount of mercury trapped by the sorbent bed per unit mass of the adsorbent material. Mercury removal capacity is typically expressed in mg of mercury trapped per gram of adsorbent material (mg · g ⁻¹ ).

A typical test reference flue gas (referred to herein as RFG1) has the following composition by weight: O ₂ 5%; CO ₂ 14%; SO ₂ 1500 ppm; NO _x 300 ppm; HCl 100 ppm Hg 20-25 μg · m ⁻³ ; N ₂ balance; where NO _x is a combination of NO ₂ , N ₂ O and NO; Hg is elemental mercury (Hg (0), 50-60 mol%) and It is a combination of mercury oxide (40-50 mol%). In certain embodiments, the sorbent body is at least 90%, at least 91%, at least 92%, at least 95%, at least 97%, at least 98%, at least 99% or at least 99.5% initial mercury with respect to RFG1. Has removal efficiency.

In certain embodiments, the adsorbent advantageously has a high concentration of HCl, a low concentration of HCl, etc., O ₂ 5%; CO ₂ 14%; SO ₂ 1500 ppm; NO _x 300 ppm; Hg 20-25 μg • High initial mercury removal efficiency of at least 90% for flue gas containing m- ³ . “High concentration HCl” means that the HCl concentration in the gas to be treated is at least 20 ppm. “Low concentration HCl” means that the HCl concentration in the gas to be treated is at most 10 ppm. Adsorbent of a specific embodiment, the following _{composition: O 2 5%; CO 2} 14%; SO 2 1500ppm; having N _{2 balance,; NO x 300ppm; HCl 5ppm} ; Hg 20~25μg · m -3 Initial mercury removal of at least 90%, at least 91%, at least 93%, at least 95%, at least 96%, at least 98%, at least 99%, or at least 99.5% for flue gas (referred to as RFG2) Have efficiency.

  The high mercury removal efficiency of these embodiments for low HCl flue gas is particularly advantageous compared to the prior art. Prior art methods involving the injection of activated carbon powder typically require the addition of HCl to the flue gas to obtain sufficient initial mercury removal efficiency. Embodiments that provide high mercury efficiency at low HCl concentrations allow for efficient and effective removal of mercury from the flue gas stream without the need for injection of HCl into the gas stream.

In certain embodiments, the sorbent body has a high concentration of SO ₃ (5 ppm, 8 ppm, 10 ppm, 15 ppm, 20 ppm, 30 ppm, 40 ppm, etc.) and a low concentration of SO ₃ (0.01 ppm, 0.1 ppm,. 5% for O ₂ 5%; CO ₂ 14%; SO ₂ 1500 ppm; NO _x 300 ppm; Hg 20-25 μg · m ⁻³ , high initial of at least 91% Has mercury removal efficiency. “High concentration of SO ₃ ” means that the SO ₃ concentration in the gas to be treated is at least 3 ppm by weight. “Low concentration SO ₃ ” means that the SO ₃ concentration in the gas to be treated is less than 3 ppm. Adsorbents of certain embodiments have the following composition: O ₂ 5%; CO ₂ 14%; SO ₂ 1500 ppm; NO _x 300 ppm; SO ₃ 5 ppm; Hg 20-25 μg · m ⁻³ ; N ₂ balance For flue gas (referred to as RFG3), it is advantageous to have a high initial mercury removal efficiency of at least 90%, at least 91%, at least 95%, at least 98%, or at least 99%. The high mercury removal efficiency of certain embodiments for high SO ₃ flue gas is particularly advantageous compared to the prior art. Prior art methods involving injection of activated carbon powder typically require SO ₃ to be removed from the flue gas in order to obtain sufficient initial mercury removal efficiency. Embodiments that provide high mercury efficiency at high SO ₃ concentrations allow for efficient and effective removal of mercury from the flue gas stream without the need for prior removal of SO ₃ from the gas stream .

According to certain embodiments, the adsorbent has an Hg removal capacity of 0.05 mg · g ⁻¹ for RFG1, and in certain embodiments, at least 0.10 mg · g ^{−1 for} RFG1, at least 0 .15mg · g ^-1, at least 0.20 mg · g ^-1, at least 0.25 mg · g ^-1, at least 0.30 mg · g ^-1, at least 0.50 mg · g ^-1, at least 1.0 mg · g ^{- 1} , at least 2.0 mg · g ⁻¹ , or at least 3.0 mg · g ⁻¹ .

According to certain embodiments, the adsorbent has an Hg removal capacity of 0.05 mg · g ⁻¹ for RFG2, and in certain embodiments, at least 0.10 mg · g ⁻¹ , at least 0 for RFG2. .15mg · g ^-1, at least 0.20 mg · g ^-1, at least 0.25 mg · g ^-1, at least 0.30 mg · g ^-1, at least 0.50 mg · g ^-1, at least 1.0 mg · g ^{- 1} , at least 2.0 mg · g ⁻¹ , or at least 3.0 mg · g ⁻¹ . Thus, the sorbent bodies according to these embodiments have a high mercury removal capacity for low HCl flue gas streams. This is particularly advantageous compared to prior art mercury mitigation methods.

According to certain embodiments, the adsorbent has a Hg removal capacity of 0.05 mg · g ⁻¹ for RFG3, and in certain embodiments, at least 0.10 mg · g ^{−1 for} RFG3, at least 0.15 mg · g ^-1, at least 0.20 mg · g ^-1, at least 0.25 mg · g ^-1, at least 0.30 mg · g ^-1, at least 0.50 mg · g ^-1, at least 1.0 mg · g ⁻¹ , at least 2.0 mg · g ⁻¹ , or at least 3.0 mg · g ⁻¹ . Thus, the sorbent bodies according to these embodiments have a high mercury removal capacity for high SO ₃ flue gas streams. This is particularly advantageous compared to prior art mercury mitigation methods.

Accordingly, a further embodiment of the invention is any of the adsorbents described herein, wherein the adsorbent has an initial mercury removal efficiency of at least 90% with respect to RFG1, RFG2, and / or RFG3. Or the adsorbent has a mercury removal capacity of at least 0.05 mg · g ⁻¹ for RFG1, RFG2 and / or RFG3.

In view of the above, embodiments of the present invention
Activated carbon,
Sulfur in any oxidation state as elemental sulfur or in a compound or moiety containing sulfur; and
A metal catalyst in any oxidation state as a metal element or in a compound or moiety containing a metal;
Including
The adsorbent has an initial mercury removal efficiency of at least 90% with respect to RFG1, RFG2 and / or RFG3;
It is an adsorbent . For example, the sorbent body may have an initial mercury removal efficiency of at least 91%, at least 95%, at least 98%, or at least 99% with respect to RFG1, RFG2, and / or RFG3. Sulfur and / or metal catalysts may be dispersed throughout the activated carbon matrix in some embodiments. In other embodiments, the sulfur and / or metal catalyst is not dispersed throughout the activated carbon matrix. The sorbent body of this embodiment has any one or more other features mentioned for any other sorbent body of the present invention, including the features of activated carbon, sulfur, and metal catalysts described above. Can also have.

Further embodiments of the present invention are:
Activated carbon,
Sulfur in any oxidation state as elemental sulfur or in a compound or moiety containing sulfur; and
A metal catalyst in any oxidation state as a metal element or in a compound or moiety containing a metal;
An adsorbent containing
Here, the adsorbent has a mercury removal capacity of at least 0.05 mg · g ⁻¹ with respect to RFG1, RFG2 and / or RFG3. For example, adsorbents, RFG1, with respect RFG2 and / or RFG3, at least 0.10 mg · g ^-1, at least 0.15 mg · g ^-1, at least 0.20 mg · g ^-1, at least 0.25 mg · g ^-1 Mercury removal capacity of at least 0.30 mg · g ⁻¹ , at least 0.50 mg · g ⁻¹ , at least 1.0 mg · g ⁻¹ , at least 2.0 mg · g ⁻¹ , or at least 3.0 mg · g ⁻¹ Can be included. Sulfur and / or metal catalysts can be dispersed throughout the activated carbon matrix in some embodiments. In other embodiments, the sulfur and / or metal catalyst is not dispersed throughout the activated carbon matrix. The adsorbent of this embodiment also has one or more other features mentioned for any other adsorbent of the present invention, including the features of activated carbon, sulfur, and metal catalysts described above. May be included.

Another aspect of the present invention is a method for the removal of toxic substances from a fluid comprising the step of contacting a fluid containing toxic substances with an adsorbent according to the present invention. Toxic substances include cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic, and selenium, wherein the toxic substance is in any oxidation state. However, it may be in the form of an element or a compound containing the element. The adsorbent can be used to treat fluid streams, including gas streams and fluid streams containing toxic substances such as arsenic, cadmium, mercury and / or selenium, for example, to reduce toxic substances. These methods typically comprise placing an adsorbent in the fluid stream. These treatment methods are particularly advantageous for reducing mercury from the fluid stream.

Due to the ability to remove elemental mercury from the fluid, a particularly advantageous embodiment of the method comprises the step of placing the adsorbent in a gaseous stream comprising mercury, wherein at least 10 mol%, At least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol% or at least 70 mol% mercury is present in the elemental state.

Due to the ability to remove elemental mercury from the fluid, a particularly advantageous embodiment of the method is less than 50 ppm by weight and less than 40 ppm by weight, even when the gas stream contains very low concentrations of HCl. Placing the adsorbent in a gaseous stream comprising HCl at an HCl concentration of less than 30 ppm, less than 20 ppm, or less than 10 ppm.

Due to the ability to remove elemental mercury from the fluid, a particularly advantageous embodiment of the method, even if the gas stream contains a high concentration of SO ₃ , is a mercury and SO ₃ concentration of at least 3 ppm by weight. Certain embodiments comprise placing the adsorbent in a gas stream comprising SO ₃ at a SO ₃ concentration of greater than 5 ppm, greater than 8 ppm, greater than 10 ppm, or greater than 20 ppm.

A further aspect of the present invention is a method for preparing an adsorbent comprising :
(A) providing a batch mixture in the form of a batch mixed material comprising a carbon source material, a sulfur source material, a metal catalyst source material and an optional filler material, wherein the metal catalyst source material is in the mixture A substantially homogeneous dispersion step;
(B) carbonizing the batch mixture;
(C) activating the carbonized batch mixture;
It has.

In certain embodiments, the carbon source material is a synthetic carbon-containing polymer material; activated carbon powder; charcoal powder; coal tar pitch; petroleum pitch; wood flour; cellulose and its derivatives; natural organic materials such as wheat flour; , Corn flour, nut shell powder; starch; coke; coal; or any mixture or combination of any two or more thereof. All these materials contain certain components that contain carbon atoms in molecular level structural units that can be retained at least in part in the final activated carbon matrix of the sorbent body. According to a particular embodiment, the carbon source material comprises a phenolic resin or a furfuryl alcohol-based resin.

  In one embodiment, the synthetic polymeric material can be a synthetic resin in the form of a solution or a low viscosity liquid at ambient temperature. Alternatively, the synthetic polymeric material can be solid at ambient temperature, but has the ability to liquefy by heating or other means. Examples of useful polymeric carbon source materials include thermosetting resins and thermoplastic resins (eg, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, etc.). Further, in one embodiment, the relatively low viscosity carbon precursor (eg, thermosetting resin) may have a typical viscosity range of about 50-100 mPa · s (about 50-100 cps). preferable. In another embodiment, a high carbon yield resin can be used. For this purpose, “high carbon yield” means that greater than about 10% of the initial weight of the resin is converted to carbon upon carbonization. In another embodiment, the synthetic polymeric material can include a furfural alcohol-based resin such as a phenolic resin or a furan resin. Phenolic resins are preferred because of their low viscosity, high carbon yield, high degree of crosslinking during curing compared to other precursors, and low cost. A typical suitable phenolic resin is a resole resin such as a plyophen resin. A typical suitable furan liquid resin is Furcab-LP commercially available from QO Chemicals Inc. (USA). Typical solid resins that are suitable for use as synthetic carbon precursors are phenolic resins or novolacs. Furthermore, it should be understood that a mixture of novolac and one or more resole resins can also be used as a suitable polymeric carbon source material. Since the phenolic resin forms a batch mixed material, it can be pre-cured or uncured when mixed with other materials. When the phenolic resin is precured, the precured material can include pre-incorporated sulfur, a metal catalyst, or an optional inorganic filler. In certain embodiments, it is desirable to include a curable, uncured resin as part of the carbon source material in the batch blend material. Thermoplastic or thermosetting curable materials undergo higher reactions when subjected to specific reactions such as chain growth and crosslinking when subjected to curing conditions such as mild heat treatment, irradiation, and chemical activation. A curable material having a degree is formed.

  In certain embodiments, the organic binder typically used in extrusion and / or injection molding processes can also be part of the carbon source material. Typical binders that can be used are plasticized organic binders such as cellulose ethers. Typical cellulose ethers include methyl cellulose, ethyl hydroxyethyl cellulose, hydroxybutyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose sodium salt, and the like Of the mixture. Furthermore, cellulose ethers such as methylcellulose and / or methylcellulose derivatives are particularly suitable as organic binders with methylcellulose, hydroxypropyl methylcellulose, or a combination of preferred ones. An example of a methylcellulose binder is METHOCEL A sold by Dow Chemical Company. An example of a hydroxypropyl methylcellulose binder is METHOCEL E, F, J, K, also sold by Dow Chemical Company. A METHCEL 310-based binder, also sold by Dow Chemical Company, can also be used in connection with the present invention. METHOCEL A4M is an example of a binder for use with a RAM extruder. METHOCEL F240C is an example of a binder for use with a twin screw extruder.

  Carbonizable organic fillers can be used as part of the carbon source material in certain embodiments of the method. Typical carbonizable fillers include natural and synthetic, hydrophobic and hydrophilic, fibrous and non-fibrous fillers. For example, some natural fillers include conifers such as pine, spruce, cedar, etc .; hardwoods such as ash, beech, birch, maple, oak, etc .; sawdust, shell fibers such as powdered almond shell, coconut shell, Apricot seed shell, peanut shell, pecan shell, walnut shell, etc .; cotton fiber, eg cotton flock, cotton fabric, cellulose fiber, cottonseed fiber; chopped plant fiber, eg hemp, coconut fiber, jute, sisal hemp And other ingredients such as corn cobs, citrus pulp (dried), soybean meal, peat moss, flour, corn, potato, rice, tapioca. Some synthetic materials are regenerated cellulose, rayon fiber, cellophane and the like. One particularly suitable carbonizable fiber filler is a cellulose fiber such as that supplied by International Filler Corporation (North Tonawanda, NY, USA). This material has the following sieve analysis: 1-2% pass at 40 mesh (420 μm), 90-95% pass at 100 mesh (149 μm), and 55-60% pass at 200 mesh (74 μm). Some hydrophobic organic synthetic fillers are polyacrylonitrile fiber, polyester fiber (floc), nylon fiber, polypropylene fiber (floc) or powder, acrylic fiber or powder, aramid fiber, polyvinyl alcohol, and the like. Such organic fibrous fillers are partly as part of the carbon source material, partly as a mechanical property enhancer for batch mixtures and partly during carbonization. It can function as a pore former where the portion will volatilize.

Non-limiting examples of metal catalyst source materials include: alkali and alkaline earth halides, oxides and hydroxides; vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver, Tungsten and lanthanoid oxides, sulfides, and salts. The metal element in the metal catalyst source material can have various valences. For example, when iron is included in the metal catalyst source material, it exists as a valence of +3, +2 or 0, or as a mixture of various valences, and the metal iron (0), FeO, Fe ₂ O ₃ , Fe ₃ O ₈ , FeS, FeCl ₂ , FeCl ₃ , FeSO _{4 and the} like. In another example, when manganese is present in the metal catalyst source, metal manganese (0), MnO, MnO ₂ , MnS, MnCl ₂ , MnCl _{4 with} a valence of +4, +2 or 0, or a mixture of various valences. , MnSO _{4 and the} like.

According to a particular embodiment, the metal catalyst source material is:
(I) alkali and alkaline earth metal halides and oxides;
(Ii) noble metals and their compounds;
(Iii) vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver, tungsten and lanthanoid oxides, sulfides and salts; or (iv) (i), (ii) and It exists in a form selected from two or more combinations and mixtures of (iii). According to a particular embodiment of the method, the metal catalyst source material is:
(I) Manganese oxides, sulfides, sulfates, acetates and salts; (ii) Iron oxides, sulfides and salts;
(Iii) a combination of (i) and KI;
(Iv) a combination of (ii) and KI; and / or (v) present in a form selected from a mixture and combination of any two or more of (i), (ii), (iii) and (iv) .

 Non-limiting examples of sulfur source materials include: sulfur powder; sulfur-containing powdered resin; sulfide; sulfate; and other sulfur-containing compounds; or any two or more mixtures or combinations thereof. Typical sulfur-containing compounds are hydrogen sulfide and / or its salts, carbon disulfide, sulfur dioxide, thiophene, sulfur anhydrides, sulfur halides, sulfates, sulfites, sulfacids, sulfatols, sulfamic acids, sulfans, It may include sulfanes, sulfuric acid and its salts, sulfites, sulfonic acids, sulfobenzides, and mixtures thereof. When using elemental sulfur powder, in one embodiment it is preferred to have an average particle size not exceeding about 100 μm. Furthermore, in certain embodiments, it is preferred that the elemental sulfur powder has an average particle size not exceeding about 10 μm.

  Inorganic fillers are not required to be present in the batch mix material. However, if present, the filler material can be, for example: oxide glass; oxide ceramics; or other refractory materials. Typical inorganic fillers that can be used include clays, zeolites, oxygen-containing minerals such as talc or their salts, carbonates such as calcium carbonate, aluminosilicates such as kaolin (aluminosilicate clay), fly ash ( Aluminosilicate ash obtained after coal combustion in power plants), eg wollastonite (calcium metasilicate), titanate, zirconate, zirconia, zirconia spinel, aluminum silicate magnesium mullite, alumina, alumina trihydrate Silicate, boehmite, spinel, feldspar, attapulgite, and silicates such as aluminosilicate fiber, cordierite powder, mullite; cordierite; silica; alumina; other oxide glasses; other oxide ceramics; or other refractory materials Is .

 Some examples of particularly suitable inorganic fillers are cordierite powder, talc, clay, and Fiberfax brands such as Carbonundum Co. Aluminosilicate fibers as provided by (Niagara Falls, NY, USA), and combinations thereof. Fiberfax aluminosilicate fibers are measured to be about 2-6 μm in diameter and about 20-50 μm in length. Further examples of inorganic fillers include various carbides such as silicon carbide, titanium carbide, aluminum carbide, zirconium carbide, boron carbide, and aluminum-titanium carbide; baking soda, nacoite, calcite, hanksite and liotite Carbonates or carbonate-containing minerals; and nitrides such as silicon nitride.

 The batch mixing material can optionally include a foaming aid. Typical foaming aids include soaps, fatty acids such as oleic acid, linoleic acid, polyoxyethylene stearate, etc., or combinations thereof. In one embodiment, sodium stearate is a preferred foaming aid. The optimized amount of optional extrusion aid will depend on the composition and binder. Other additives useful for improving batch extrusion and curing characteristics are phosphoric acid and oil. Phosphoric acid improves the cure rate and increases the adsorption capacity. When included, phosphoric acid is typically about 0.1% to 5% by weight in the batch mix. Furthermore, the addition of oil can aid in extrusion and can result in increased surface area and porosity. For this purpose, optional oil can be added in an amount ranging from about 0.1% to 5% by weight of the batch blend material. Exemplary oils that can be used include petroleum having a molecular weight of about 250 to 1000, including paraffinic and / or aromatic and / or alicyclic compounds. So-called paraffinic petroleum mainly composed of paraffinic and alicyclic structures is preferred. These usually may contain additives such as rust inhibitors or antioxidants as are present in commercially available oils. Some useful oils are 3M Co. 3 in 1 oil, or Reckitt and Coleman Inc. Is a 3 in 1 household oil commercially available from Wayne, NJ, USA, and other useful oils include poly (α-olefin) based synthetic oils, esters, polyalkylene glycols, polybutenes, silicones, Polyethyl ether, CTFE oil, and other commercially available oils. Vegetable oils such as sunflower oil, sesame oil, peanut oil, soybean oil are also useful. Particularly suitable are oils having a viscosity of about 10-300 Pa · s (about 10-300 cps), preferably about 10-150 Pa · s (about 10-150 cps).

The batch blend material can optionally also include natural and / or synthetic pore formers. The pore former can then be removed, for example, before or during carbonization and / or activation of the adsorbent . Removal of the pore former can give certain features to the pore structure of the sorbent body, such as spaces of various sizes and dimensions.

In one embodiment, typical pore formers may include natural or synthetic pore formers that burn out upon carbonization of the sorbent body, leaving little or no residue in the sorbent body. Examples of pore formers include polymeric materials such as polymer beads. Examples of polymer materials such as polymer beads include polypropylene and polyethylene materials and beads. In one embodiment, the batch blend material is decomposed under a inert atmosphere at high temperature (> 400 ° C.) as a pore former, leaving little or no residue, such as polypropylene, polyester or acrylic powder or fiber, etc. Can be included.

Additional pore formers include natural and synthetic starches. In some embodiments, when the pore former is water soluble, such as starch, the pore former may be removed after curing the adsorbent through dissolution of water prior to carbonization. In another embodiment, a suitable pore forming agent can be characterized by forming macropores due to particle expansion. For example, graphite intercalation compounds containing acids such as hydrochloric acid, sulfuric acid or nitric acid form macropores upon heating due to the resulting expansion of the acid. Furthermore, macropores can also be formed by dissolving certain temporary materials. For example, baking soda, calcium carbonate or limestone particles having a particle size corresponding to the desired pore size can be extruded with a carbon material to form a monolithic adsorbent. Baking soda, calcium carbonate or limestone forms a water-soluble oxide during the carbonization and activation process, which is substantially filtered by immersing the monolithic adsorbent in water, The pores are formed.

In order to provide a dispersion of the metal catalyst throughout the final adsorbent , it is highly desirable that the carbon source material and the metal catalyst source material be intimately mixed to form a batch mixed material. Thus, in certain embodiments, various source materials are provided in the form of fine powders or solutions where possible, and then intimately mixed by using an effective mixing device. It is desirable. Where powders are used, certain embodiments are provided with an average size not exceeding 100 μm, in certain other embodiments not exceeding 10 μm, in certain other embodiments 1 μm No more than will be provided.

  A variety of equipment and methods may be used to form the batch mix material into a batch mix of the desired shape. For example, the batch mixture can be molded using extrusion molding, injection molding (including reactive injection molding), compression molding, casting, pressure molding, or rapid prototyping. For example, when the object is formed by injection molding or compression molding, the object may be cured as it is. Alternatively, the object can be cured after molding, for example when molded by extrusion, casting, or rapid prototyping. According to some embodiments, the extruded batch mixture or cured batch mixture is in the form of a monolithic honeycomb having a plurality of channels.

Extrusion is particularly preferred in certain embodiments where the batch mix material is formed into a desired shape batch mix. Extrusion using standard extruders (ram extruders, single screw extruders, twin screw extruders, etc.) and special extrusion molds, honeycombs, pellets, rods, spaghettis, etc. Adsorbents with various forms and shapes can be made. Extrusion is particularly effective in producing monolithic honeycomb bodies having a plurality of hollow channels that can serve as fluid passages. Extrusion is advantageous in that very intimate mixing of all raw materials can be achieved during the process.

  Molds of various shapes and dimensions can also be used to form batch materials through injection molding, compression molding, and casting, all of which are well known molding techniques. Rapid prototyping, which is the automatic creation of physical objects using solid freeform fabrication, may also be used to form batch materials. One advantage of rapid prototyping is that it can be used to create virtually any shape or form. Rapid prototyping is a computer-aided design that transforms a design into a virtual thin horizontal section, and then creates each section of the design in physical space from one to the next until its shape is complete Including obtaining a design. One embodiment includes the steps of obtaining a virtual design of the molded batch material, converting the design into a virtual thin horizontal cross section, and creating each cross section in the physical space obtained from the batch material. Do it. One example of rapid prototyping is 3D printing.

In certain embodiments, it is desirable for the batch mix material to include an uncured curable material. In those embodiments, during the formation of the batch mixture, the adsorbent is typically subjected to a heat treatment such that, for example, the curable component is cured, resulting in the formation of a cured batch mixture. It is subjected to curing conditions. The cured batch mixture tends to have better mechanical properties than the uncured predecessor and is therefore easier to handle in subsequent process steps. Further, while not intending to be bound by a particular theory, or need to do so, the curing process results in a carbon network during the subsequent carbonization and activation process. It is believed that a network of polymers having a carbon skeleton that can facilitate formation can be provided. In certain embodiments, curing is generally performed by heating the molded batch mixture at a temperature of 70 ° C. to 200 ° C. for about 0.5 to about 5.0 hours in air at atmospheric pressure. Is done. In certain embodiments, the batch mixture is heated stepwise from low to higher, for example from 70 ° C. to 90 ° C., to 125 ° C., to 150 ° C., each temperature being held for a certain period of time. . Alternatively, when using certain precursors (eg, furfuryl alcohol or furan resin), curing can also be achieved by adding a curing additive such as an acid additive at room temperature. Curing, in one embodiment, can serve to maintain the homogeneity of the metal catalyst dispersion in the carbon.

After formation of the batch mixture, its drying, or its optional curing, the shaped body is subjected to a carbonization step. For example, the batch mixture (cured or uncured) is in an atmosphere O ₂ is depleted, by subjecting the carbonization temperature to rise it can be carbonized. The carbonization temperature can be in the range of 600-1200 ° C, and in certain embodiments is in the range of 700-1000 ° C. The carbonization atmosphere may be inert and mainly includes non-reactive gases such as N ₂ , Ne, and Ar, a mixture thereof, and the like. At the carbonization temperature in an atmosphere depleted of O _{2, the} organic material contained in the batch mixture is decomposed to release carbon residues. As expected, complex chemical reactions occur in high temperature processes. Such reactions include, among others, the following:
(I) decomposition of the carbon source material to release the carbon body;
(Ii) decomposition of the metal catalyst source material;
(Iii) decomposition of the sulfur source material;
(Iv) reaction of the sulfur source material with the carbon source material;
(V) reaction of sulfur source material with carbon;
(Vi) reaction of the sulfur source material with the metal catalyst source material;
(Vii) reaction of metal catalyst source material with carbon source material; and (viii) reaction of metal catalyst source material with carbon.

Net effects include, among others:
(1) Redispersion of the metal catalyst source material and / or metal catalyst;
(2) sulfur redispersion;
(3) Formation of sulfur elements derived from sulfur source materials (sulfates, sulfites, etc.);
(4) Formation of sulfur-containing compounds derived from sulfur source materials (such as elemental sulfur);
(5) formation of a metal catalyst in the form of an oxide;
(6) formation of a metal catalyst in the form of a sulfide;
(7) Reduction of part of the metal catalyst source material. Part of the sulfur (particularly in the elemental state) and part of the metal catalyst source material (such as KI) can be swept away by the carbonization atmosphere during carbonization.

The carbonization process results in a carbon body in which sulfur and the metal catalyst are dispersed. However, this carbonized batch mixture typically does not have the specific surface area desired for effective adsorption of toxic materials. In order to obtain a final adsorbent having a high specific surface area, the carbonized batch mixture is further activated. Carbonized batch mixture, for example, CO _2, H ₂ O, CO ₂ and H ₂ O mixture, a mixture of CO ₂ and nitrogen, H ₂ mixture of O and nitrogen, and CO ₂ and other inert gases It may be activated under a gas atmosphere selected from the group consisting of, for example, at an elevated activation temperature in a CO ₂ and / or H ₂ O containing atmosphere. The atmosphere is substantially pure CO ₂ or H ₂ O (vapor), a mixture of CO ₂ and H ₂ O, or CO ₂ and / or H ₂ O and an inert gas such as nitrogen and / or argon. It may be a combination. The use of a combination of nitrogen and CO ₂ can lead to cost savings, for example. A mixture of CO ₂ and nitrogen can be used, for example, with a low CO ₂ content of 2% or more. Typically, to reduce process costs, a mixture of CO ₂ and nitrogen having a CO ₂ content of 5-50% may be used. The activation temperature can range from 600 ° C to 1000 ° C, and in certain embodiments ranges from 600 ° C to 900 ° C. During this process, part of the carbon structure of the carbonized batch mixture is gently oxidized:

It results in the etching of the structure of the carbon body and the formation of an activated carbon matrix that defines multiple pores in the nanoscale and microscale. Activation conditions (time, temperature, and atmosphere) can be adjusted to produce a final product with the desired specific surface area and composition. Similar to the carbonization process, the high temperature of the activation process results in complex chemical reactions and physical changes. It is highly desirable that the metal catalyst is dispersed throughout the activated carbon matrix at the end of the activation process. It is highly desirable that at the end of the activation process, the metal catalyst is substantially homogeneously dispersed throughout the activated carbon matrix. It is highly desirable that at the end of the activation step, the metal catalyst is present in at least 30%, at least 40%, at least 50%, at least 60%, or at least 80% of the pore wall surface area. At the end of the activation process, it is highly desirable that the sulfur be dispersed throughout the activated carbon matrix. It is highly desirable that at the end of the activation process, the sulfur is substantially homogeneously dispersed throughout the activated carbon matrix. It is highly desirable that at the end of the activation process, sulfur is present in at least 30%, at least 40%, at least 50%, at least 60%, or at least 80% of the pore wall surface area.

According to a particular embodiment, the batch mixed material, after activation, has an adsorbent of less than 20% by weight of inorganic material other than carbon, sulfur and metal catalyst (in certain embodiments less than 10%, certain In other embodiments less than 5%).

According to certain embodiments, the batch mixture material, after activation, has an adsorbent of 30 wt% to 50 wt% based on the total weight of carbon, sulfur, and metal catalyst, in addition to carbon, sulfur, and metal catalyst. Selected to include inorganic material.

In certain embodiments of the method of the present invention, all metal catalyst source materials and all sulfur source materials are batched by in-situ formation, such as in-situ extrusion, casting. Contained in the mixture. This method is notably:
(A) avoids subsequent processes (such as impregnation) of filling the metal catalyst and / or sulfur on the activated carbon body, thereby reducing process steps, possibly increasing all process yields and reducing process costs And
(B) typically than those obtained by impregnation results in a distribution of more homogeneous active adsorption sites (metal catalyst and sulfur) in the adsorber,
Of (c) a metal catalyst and sulfur, durable, resulted in a strongly fixed to the adsorbent, the adsorbent, while the long-term use, to be able to withstand the flow of the fluid stream to be processed,
Has the advantage. Impregnation can result in selective dispersion of species (such as metal catalyst and sulfur) impregnated on the outer cell walls, large pores on the wall surface (such as those on the micrometer scale). Filling impregnated seeds onto wall surfaces with a high proportion of nanoscale pores can be time consuming and difficult. Most of the surface area of activated carbon with a high specific surface area of 400-2000 m ² · g ⁻¹ is due to nanoscale pores. Thus, for a typical impregnation process, it would be difficult to provide a large portion of the specific surface area of such an activated carbon material with the impregnated seed filling. Furthermore, a typical impregnation step results in a thick, relatively dense layer of impregnated species on the outer cell wall and / or wall surface where large pores are present, thereby reducing the size of the smaller pores or This is considered to result in effectively reducing the adsorption function of the activated carbon by blocking the passage of the outside fluid. Furthermore, the immobilization of the impregnated species in the adsorbent in a typical impregnation process is mainly due to relatively weak physical forces and may be insufficient for long term use in fluid flow.

  Nevertheless, in certain embodiments, it is not necessary that all metal catalyst and / or sulfur be substantially homogeneously dispersed throughout the activated carbon matrix. In these embodiments, not all metal catalyst source material and sulfur source material are formed in situ into the batch mixture. It is contemplated that after the activation step, a specific metal catalyst and / or sulfur impregnation step is performed. Alternatively, after the activation step, a step of treating the activated body with a sulfur-containing and / or metal catalyst-containing atmosphere may be performed. Such post-activation metal catalyst loading is particularly useful for metals that cannot withstand carbonization and / or carbonization processes, such as those based on organometallic compounds such as iron acetylacetonate.

Once the activated adsorbent of the present invention is formed, it can be subjected to post-finishing steps such as pelletizing, grinding, and assembly by stacking. The adsorbents of various shapes and compositions of the present invention can then be packed into a fixed bed that is placed in the absence of fluid flow to be treated.

Another aspect of the present invention is an extruded batch mixture,
(I) a carbon source material comprising an uncured, curable polymer resin;
(II) particles of sulfur-containing material;
(III) a metal catalyst in any form of an element or a compound containing a metal;
Including
Here, the metal catalyst is substantially homogeneously dispersed in the material forming the extruded batch mixture.

  According to certain embodiments of the extrusion batch mixture of the present invention, the particles of sulfur-containing material are substantially homogeneously dispersed in the material forming the extruded batch mixture.

  According to a particular embodiment of the extrusion batch mixture of the present invention, the sulfur-containing material comprises at least 50 mol% elemental sulfur.

According to certain embodiments of the extrusion batch mixture of the present invention, the sulfur-containing material comprises elemental sulfur, sulfate, sulfite, sulfide, CS ₂ , and other sulfur-containing compounds.

According to certain embodiments of the extrusion batch mixture of the present invention, the extruded batch mixture further comprises:
(IV) a binder material; and / or (V) an inorganic filler material; and / or (VI) a lubricant.

  According to a particular embodiment, the extruded batch mixture contains less than 20% by weight of inorganic material in addition to carbon, sulfur-containing inorganic material, water and metal catalyst. In certain embodiments it is less than 10% and in certain other embodiments it is less than 5%.

  According to certain embodiments, the extruded batch mixture includes 20 wt% to 50 wt% inorganic material in addition to carbon, sulfur-containing inorganic material, water and metal catalyst. In certain embodiments, the material is a chemically stable, refractory inorganic material at 800 ° C. and in certain other embodiments at 1000 ° C.

  According to certain embodiments, the extruded batch mixture is selected from cordierite, mullite, silica, alumina, other oxide glasses, other oxide ceramics, other refractory materials, and mixtures and combinations thereof Heat resistant inorganic material. According to certain embodiments, the refractory inorganic material includes microscale pores.

  The invention is further illustrated by the following non-limiting examples.

Example 1
46% liquid phenolic resole resin, 1% lubricant, 13% cordierite powder, 9% sulfur powder, 7% iron acetylacetonate, 18% cellulose fiber, 5% Methocel binder and 1 The extrusion composition was formulated with% sodium stearate. This mixture was mixed and then extruded. The extruded honeycomb was then dried and cured in air at 150 ° C., then carbonized in nitrogen and activated with carbon dioxide. The activated carbon honeycomb samples were then tested for mercury removal capability. The test was performed at 160 ° C. using an elemental mercury concentration at the inlet of 22 μg · m ⁻³ . Carrier gas for mercury contained N _2, SO _2, O ₂ and CO _2. The gas flow rate was 750 ml / min. Total mercury removal efficiency was 86%, while elemental mercury removal efficiency was 100%.

Example 2
Another extrusion composition was extruded as in Example 1, except that 12% cordierite powder was used instead of 13%, 4% iron acetylacetonate instead of 7% iron acetylacetonate and 4%. % Potassium iodide was used. After activation, these samples showed 90% total mercury removal and 100% elemental mercury removal. Therefore, the presence of KI in the composition improved efficiency.

Example 3
In this experiment, the composition of the extrudate was 59% phenolic resole resin, 1% phosphoric acid, 1% oil, 9% sulfur powder, 3% iron oxide, 19% cellulose fiber, 7% % Methocel binder and 1% sodium stearate. These samples were extruded, cured, carbonized, activated, and tested for mercury removal performance as in Example 1. Mercury removal efficiencies were 87% and 97% for total mercury and elemental mercury, respectively.

Example 4
In this experiment, 6% MnO ₂ , 13% cordierite, 7% sulfur, 19% cellulose fiber, 5% methocel binder, 1% sodium stearate, 47% phenolic resole resin, 1% Manganese oxide was used as the metal catalyst source with a composition of 1% phosphoric acid and 1% oil. The mercury removal efficiency of the sample based on this composition was 92% and 98% for total mercury and elemental mercury, respectively.

Example 5
In the examples, sulfur was added as MnS instead of elemental sulfur in combination with manganese. The composition was 15% cordierite, 10% MnS, 20% cellulose fiber, 5% methocel binder, 1% sodium stearate, 47% phenolic resole resin, and 1% oil.

  In curing, carbonization and activation, the mercury removal efficiency of these honeycombs was 84% and 93% for total mercury and elemental mercury, respectively.

Example 6
The experiment of Example 5 was repeated using molybdenum disulfide (MoS ₂ ) instead of MnS. These samples gave 90% and 96% mercury removal efficiency for total mercury and elemental mercury, respectively.

These examples show that the sorbent body of the present invention can demonstrate high mercury removal efficiency. The adsorbents of the present invention also contain cadmium, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and the like from fluids such as flue gas and coal gasification It is expected to be useful for the adsorption of other toxic substances such as selenium.

Example 7
In this experiment, the composition of the extrudate was 14% charcoal, 47% phenolic resin, 7% sulfur, 7% manganese oxide, 18% cellulose fiber, 5% mytical binder and 1% It was sodium alone (separate). These samples were extruded, cured, carbonized and activated as in Example 1.

The sample was then tested for mercury removal capability. The test was carried out at 140 ° C. using an elemental mercury concentration at the inlet of 24 μg / m ³ . The carrier gas for mercury contained N ₂ , HCl, SO ₂ , NO _x , O ₂ and CO ₂ . The gas flow rate was 650 ml / min. Mercury removal efficiency was 100% and 99% for both total mercury and elemental mercury. See Table II below.

Example 8
In this example, the composition of the extrudate was 16% cured sulfur-containing phenolic resin, 45% phenolic resin, 8% sulfur, 7% manganese oxide, 18% cellulose fiber, 4% mytical bond. Agent and 1% sodium alone. These samples These samples were extruded, cured, carbonized and activated as in Example 1.

  Activated carbon samples were tested as in Example 7. Mercury removal efficiency was 100% and 99% for both total mercury and elemental mercury. See Table III below. Thus, both Examples 7 and 8 achieved excellent mercury removal results.

ここで、それぞれ、所定の試験時間における、Ｃ₀はＨｇ（ｘ）の流入口濃度であり、Ｃ₁はＨｇ（ｘ）の流出口濃度である。 Various adsorbents with different components were tested for mercury removal efficiency. The test results are listed in Table I below. In all tables and drawings in this application, Hg ⁰ or Hg (0) means elemental mercury; Hg ^T or Hg (T) means total mercury including element and mercury oxide, Eff (Hg ⁰ ) or Eff (Hg (0)) means instantaneous mercury removal efficiency for elemental mercury, and Eff (Hg ^T ) or Eff (Hg (T)) is the instantaneous mercury removal efficiency for mercury in all oxidation states. means. As above, Eff (Hg (x)) is calculated as follows:

Here, at a predetermined test time, C ₀ is the inlet concentration of Hg (x), and C ₁ is the outlet concentration of Hg (x).

  Comparison of sample numbers C and D in Table I shows that the adsorbent material containing MnS tends to have higher performance when the batch mixture material contains elemental sulfur than when the batch mixture material does not contain elemental sulfur. It clearly shows that there is.

FIG. 1 is a graph comparing the mercury removal ability of an adsorbent test sample according to the present invention and the time course of a comparative adsorbent. The left vertical axis is the total amount of mercury (MSS, mg · g ⁻¹ ) per unit mass captured by the test sample of the adsorbent tested. The right vertical axis is the instantaneous mercury removal efficiency (Eff (Hg)) of the adsorbent tested, which is the instantaneous total mercury removal efficiency measured and calculated according to the above equation. The horizontal axis is the time when the sample was exposed to the test gas. Some Eff (Hg) data in this figure is also included in Table III below. The adsorbent according to the present invention comprises sulfur, in situ extruded MnO ₂ as the metal catalyst source, and about 45% by weight cordierite as the inorganic filler. Sample 2.2 is a comparative adsorbent that does not contain an in situ extruded metal catalyst source, is comparable to sulfur and cordierite, and impregnated with FeSO ₄ and KI. Curves 101 and 103 show the Eff (Hg) and MSS of the adsorbent according to the present invention, respectively. Curves 201 and 203 show the Eff (Hg) and MSS of the comparative adsorbent, respectively. As can be seen from the data in this figure and Table III, the adsorbent does not show a sharp drop in mercury removal efficiency even after 250 hours of exposure to a simulated flue gas containing about 20 μg · m ⁻³ of total mercury. It was not seen, suggesting that a significant amount of mercury could be captured by the adsorbent material until saturation (or mercury leakage point) was reached. The data in curve 201 and Table III indicate that the comparative adsorbent has a rapid continuous decline in instantaneous mercury removal efficiency for about 70 hours starting within 50 hours and ending the test, indicating early saturation of the adsorbent. It shows that Curves 103 and 203 overlap to some extent at an early stage of the test period, but 203 ends in about 69 hours.

  FIG. 1 shows that the adsorbent of this embodiment of the present invention, which includes an in-situ extruded metal catalyst source, has a much higher mercury removal, especially for a longer time, than an adsorbent with an impregnated metal catalyst source. It shows that it can have the ability. While not intending or needing to be bound by any particular theory, the superior performance of the adsorbent of the present invention is a more homogeneous dispersion of the metal catalyst and less blockage of the pores of the activated carbon matrix by the metal catalyst. This is thought to be due to the lack of

FIG. 2 is a graph showing the inlet mercury concentration (CHg0) and outlet mercury concentration (CHg1) of the adsorber , according to one embodiment of the various inlet mercury concentrations of the present invention. This graph clearly shows that the adsorbent of certain embodiments of the present invention can effectively remove mercury at various mercury concentrations (ranging from about 70 to about 25 μg · m ⁻³ ). To suggest.

FIG. 3 is an SEM image of a portion of a cross-section of an adsorbent according to the present invention comprising an in situ extruded metal catalyst. From the images, there is no selective accumulation of metal catalyst or sulfur. FIG. 4 is an SEM image of a portion of a cross-section of a comparative adsorbent containing a metal catalyst impregnated after activation. A clearly visible white layer of material on the cell walls is the impregnated metal catalyst. This relatively dense layer of metal catalyst impregnated layer can block entry into many macro-scale and nano-scale pores inside the cell wall and reduce all the performance of the comparative adsorbent. Conceivable.

It will be appreciated by those skilled in the art that various modifications and alternatives can be made to the present invention without departing from the scope and spirit of the invention. Thus, it is intended that the present invention cover modifications and variations of this invention that come within the scope of the appended claims and their equivalents.

Claims (6)

An activated carbon matrix;
Sulfur in any oxidation state as elemental sulfur or in a compound or moiety containing sulfur; and
Alkaline earth hydroxide,
A metal catalyst in any oxidation state, as a metal element or in a compound or part containing a metal,
Wherein the metal catalyst is said be dispersed throughout the activated carbon matrix, and are selected from sulfides of manganese or molybdenum, adsorbent. The adsorbent according to claim 1, wherein at least a part of the sulfur is chemically bonded to at least a part of carbon of the activated carbon matrix. The adsorbent according to claim 1, comprising elemental sulfur. One or more of the following toxic substances from the fluid in which the metal catalyst contacts the adsorbent:
Promotes removal of cadmium, mercury, chromium, lead, barium, beryllium, nickel, cobalt, vanadium, zinc, copper, manganese, antimony, silver, thallium, arsenic and selenium,
  The adsorbent according to claim 1, wherein the toxic substance is in an arbitrary oxidation state and is in the form of an element or a compound containing the element. The adsorbent according to claim 1, which is in the form of a honeycomb monolith. The adsorbent according to claim 1, wherein at least a part of the metal catalyst is chemically bonded to at least a part of the sulfur.