US20060198774A1 - Mercury Removal sorbent - Google Patents

Mercury Removal sorbent Download PDF

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Publication number
US20060198774A1
US20060198774A1 US11/071,632 US7163205A US2006198774A1 US 20060198774 A1 US20060198774 A1 US 20060198774A1 US 7163205 A US7163205 A US 7163205A US 2006198774 A1 US2006198774 A1 US 2006198774A1
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accordance
heavy metal
composition
vanadium oxide
weight
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US11/071,632
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Joseph Cross
Glenn Dodwell
Marvin Johnson
Edward Sughrue
Jianhua Yao
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ConocoPhillips Co
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ConocoPhillips Co
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Priority to US11/071,632 priority Critical patent/US20060198774A1/en
Assigned to CONOCOPHILLIPS COMPANY reassignment CONOCOPHILLIPS COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CROSS, JOSEPH B., DODWELL, GLENN W., JOHNSON, MARVIN M., SUGHRUE, EDWARD L., II, YAO, JIANHUA
Priority to PCT/US2006/006906 priority patent/WO2006096375A2/en
Publication of US20060198774A1 publication Critical patent/US20060198774A1/en
Priority to US12/175,317 priority patent/US7744763B2/en
Priority to US12/175,257 priority patent/US20080274877A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0214—Compounds of V, Nb, Ta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/911—Cumulative poison
    • Y10S210/912—Heavy metal
    • Y10S210/914—Mercury
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/515—Specific contaminant removal
    • Y10S502/516—Metal contaminant removal

Definitions

  • the invention relates to a composition and method for removing heavy metal contaminates from fluid streams.
  • the invention relates to a method of preparing such composition.
  • the invention relates to a process for removing heavy metal contaminates, such as mercury and mercury compounds, from flue gas streams produced from the combustion of hydrocarbon-containing materials.
  • Heavy metals are released during the combustion process of many fossil fuels and/or waste materials. These heavy metals include, for example, arsenic, beryllium, lead, cadmium, chromium, nickel, zinc, mercury, and barium. Most of these heavy metals are toxic to humans and animals. In particular, elemental mercury and mercury compounds such as mercury chlorides are thought to compromise the health and mental acuity of young children and fetuses.
  • a further object of this invention is to provide a method for making an improved vanadium material by incorporating a vanadium oxide compound and an alkali metal hydroxide promoter with a porous support material.
  • Another object of this invention is to provide a process for removing heavy metals or heavy metal compounds from a fluid stream by contacting the fluid stream with an improved vanadium material.
  • Yet another object of this invention is to provide an improved vanadium material which when used in the removal of heavy metals results in the oxidation of the heavy metal to an oxidation state greater than zero.
  • the inventive composition comprises a porous support material including a vanadium oxide compound and an alkali metal vanadate incorporated thereon, therein, or thereon and therein.
  • the inventive composition comprises a porous support material impregnated with a vanadium oxide compound and an alkali metal promoter selected from the group consisting of lithium hydroxide, lithium vanadate, and mixtures thereof.
  • the inventive composition can be prepared by the method of: (a) mixing a vanadium oxide compound and an alkali metal hydroxide promoter with at least one porous support material.
  • the inventive composition can be used in the removal of at least one heavy metal or heavy metal containing compound from a fluid stream by (a) contacting the fluid stream with a porous support material having incorporated onto, into, or onto and into a vanadium oxide compound and an alkali metal promoter for sorption of at least a portion of the at least one heavy metal or heavy metal containing compound.
  • the inventive composition can be used in the removal of at least one heavy metal or heavy metal containing compound from a flue gas stream produced by the combustion of a hydrocarbon-containing fuel by: (a) contacting the flue gas stream with a first sorbent material comprising a porous support having incorporated onto, into, or onto and into a vanadium oxide compound and an alkali metal promoter for sorbing at least a portion of the at least one heavy metal or heavy metal containing compound present in the flue gas stream; and (b) contacting the flue gas with a second sorbent material different from the first sorbent material for sorbing at least a portion of the at least one heavy metal-containing compound not sorbed during step (a).
  • FIG. 1 is a graph of mercury uptake versus mercury breakthrough for a lithium promoted V 2 O 5 sorbent on a porous support compared to a conventional activated charcoal sorbent;
  • FIG. 2 is a graph of the mercury removal efficiency for a lithium promoted V 2 O 5 sorbent on a porous support.
  • Compositions according to the present invention generally comprise a porous support material with a vanadium oxide compound and an alkali metal promoter incorporated thereon, therein, or thereon and therein.
  • the vanadium oxide compound comprises V 2 O 5 , a hydrate of V 2 O 5 , a peroxo complex of vanadium oxide or combinations thereof.
  • the vanadium component it is within the scope of the invention for the vanadium component to have any oxidation state greater than zero.
  • an alkali metal promoter is employed to increase the effectiveness of the vanadium oxide in sorbing heavy metals.
  • the alkali metal promoter is an alkali metal hydroxide such as lithium hydroxide.
  • the alkali metal hydroxide promoter it is possible for at least a portion of the alkali metal hydroxide promoter to react with at least a portion of the vanadium oxide compound to form an alkali metal vanadate such as lithium vanadate. Hydrates of alkali metal hydroxides can also be used such as lithium hydroxide monohydrate.
  • the promoter it is within the scope of the present invention for the promoter to be an elemental alkali metal, an alkali metal compound, or an ionic alkali metal species.
  • the term “promoter” refers to any such alkali metal composition whether it was originally added to the inventive sorbent or whether it was formed in situ.
  • the vanadium oxide compound and promoter are loaded onto a porous support material.
  • the support material is selected from the group consisting of amorphous silica-alumina, a zeolite, a material comprising meta-kaolin, alumina, expanded perlite, and combinations thereof. It is most preferable to employ a silica-alumina support material such as meta-kaolin in conjunction with expanded perlite, however, it is possible that the support may comprise pure alumina or calcined alumina.
  • the overall composition preferably comprises from about 0.5-40% by weight vanadium. Unless otherwise specified, the phrase “by weight vanadium” is defined as the elemental weight of vanadium present in the composition. More preferably, the composition comprises from about 1-35% by weight vanadium, and most preferably from about 2-25% by weight.
  • the composition preferably comprises from about 0.5-50% by weight of the alkali metal promoter, more preferably from about 1-30% by weight, and most preferably from about 5-25% by weight.
  • the weight ratio of vanadium oxide to promoter is preferably within the range of about 10:1 to 1:10, more preferably between about 5:1 to 1:5, and most preferably between about 4:1 to 1:1.
  • the sorbent material is formed by mixing a vanadium oxide compound and an alkali metal promoter with at least one porous support.
  • the vanadium oxide compound and promoter should be intimately contacted with the support so that the vanadium oxide compound and promoter become incorporated onto, into, or onto and into the support.
  • the vanadium oxide and promoter are dispensed in a first solution.
  • Water is a preferred solvent for forming this solution, however, any solvent capable of dissolving both the vanadium oxide and promoter may be used.
  • the vanadium oxide comprises from about 0.5-70% by weight of the solution, more preferably between about 5-60% by weight, and most preferably from about 10-50% by weight.
  • the promoter comprises from about 0.05-50% by weight of the solution, more preferably from about 0.5-40% by weight, and most preferably from about 1-30% by weight.
  • the porous support is dispersed in a second solution, with water being a preferred solvent.
  • an alkali metal hydroxide is selected as the promoter that is mixed with the vanadium oxide compound, generally, at least a portion of the alkali metal hydroxide reacts with at least a portion of the vanadium oxide compound to form an alkali metal vanadate, also referred to herein as a “promoter.”
  • the first and second solutions are then mixed together thereby loading the vanadium oxide and promoter onto, into, or onto and into the support.
  • the mixture is then dried, and preferably, the resulting sorbent material is in a granular or powder form. It is possible that the porous support used is not in a finely divided form prior to mixing with the vanadium oxide and promoter solution. If such is the case, it is preferable to crush and sieve the dried sorbent material to an acceptable particle size for a given application.
  • the sorbant material may also be pelletized, formed into monoliths, or incorporated into a foam in order to render it suitable for a specific application.
  • the inventive sorbent material is particularly useful in the removal of heavy metals and heavy metal containing compounds from fluid streams, especially flue gas streams produced by the combustion of hydrocarbon-containing materials such as coal and petroleum fuels.
  • fluid streams are often contaminated with at least one heavy metal or compound containing a heavy metal selected from the group consisting of arsenic, beryllium, lead, cadmium, chromium, nickel, zinc, mercury, and barium.
  • methods of removing heavy metal and heavy metal containing compounds from fluid streams comprise providing a sorbent composition according to the present invention and contacting the stream with the inventive sorbent.
  • Flue gas such as that created by the combustion of hydrocarbon-containing compounds, generally comprises at least about 10% by weight N 2 , more preferably at least about 50% by weight, and most preferably between about 75-90% by weight. Flue gas also generally comprises less than about 10% by weight of uncombusted hydrocarbons, more preferably less than about 5% by weight, and most preferably less than about 1% by weight. As described below, in a particularly preferred application, the flue gas will have already been treated for removal of NO x and SO x prior to any heavy metal removal process as the presence of high levels of NO x and SO x compounds may lead to fouling of the heavy metal removal sorbents.
  • the flue gas comprises less than about 800 ppm of SO x compounds such as SO 2 , more preferably less than about 500 ppm, and most preferably less than about 400 ppm. Also, the flue gas preferably comprises less than about 400 ppm NO x such as NO and NO 2 , more preferably less than about 250 ppm, and most preferably less than about 150 ppm. Flue gas may also comprise between about 2.5-10% by weight O 2 , between about 1-5% by weight CO 2 , and between about 5-20% by weight H 2 O.
  • the pressure drop associated with the contacting step should not exceed more than about 20 psia. More preferably, the pressure drop in the fluid stream is less than about 10 psia, and most preferably less than about 5 psia.
  • flue gas streams do not flow under high pressures. Therefore, if the pressure drop is too great, back pressure is created and can affect the combustion process by which the flue gas is created.
  • the arrangement of the sorbent material in the vessel in which contacting occurs can assist in minimizing this pressure drop.
  • the sorbent material comprises finely divided particles that are suspended in the fluid stream during the contacting step.
  • the sorbent material may be positioned in a fluidized bed, placed in a packed bed column, formed into monoliths, or incorporated into a foam.
  • pressure drop may become much more of a concern and may require the use of fans or other equipment to increase the pressure of the flue gas stream.
  • the fluid stream containing the heavy metal contaminant preferably has a temperature of between about 50-400° F. during the contacting step, more preferably between about 100-375° F., and most preferably between about 200-350° F.
  • the temperature of the fluid stream at the contacting stage is in part affected by upstream processes such as particulate removal systems (i.e., cyclones), other contaminant removal systems, heat exchange systems, etc.
  • the contacting step results in the sorption of at least about 80% by weight of the heavy metals contained in the fluid stream, more preferably at least about 90% by weight, even more preferably at least about 95% by weight, and most preferably at least about 98% by weight.
  • the vanadium oxide incorporated support material exhibits a high capacity for sorbing heavy metals and heavy metal containing compounds.
  • the vanadium oxide material is capable of sorbing at least about 1 atom of a heavy metal per every 5 atoms of vanadium. More preferably, the ratio of heavy metal atoms sorbed to vanadium atoms is at least about 1:3, and most preferably 1:1.
  • the sorbent material also exhibits the ability to oxidize the elemental heavy metal into a heavy metal containing compound such as a heavy metal oxide or chloride.
  • a heavy metal containing compound such as a heavy metal oxide or chloride.
  • the sorbent material oxidizes mercury into various oxidized species such as Hg +1 , Hg +2 , or mercury compounds such as HgO, HgCl, and HgCl 2 .
  • Hg +1 , Hg +2 mercury compounds
  • HgO, HgCl, and HgCl 2 mercury compounds
  • some of these heavy metal containing compounds may desorb or break free from the sorbent material. In that case, it can be particularly useful to employ a downstream heavy metal compound removal system in conjunction with the above-described sorbent system.
  • the gaseous product stream is contacted with a separate adsorbent in an adsorption zone.
  • the adsorbent can be any adsorbent capable of adsorbing a heavy metal; however, preferred materials for removing the heavy metal compounds include those having a hydrophobic surface with pore openings of less than about 10 ⁇ , and high pore volumes. More preferably, the adsorbent comprises, consists of or consists essentially of a material selected from the group consisting of a zeolite, amorphous carbon and combinations thereof.
  • the amorphous carbon can be an activated carbon and/or activated charcoal.
  • Exemplary zeolites include those with 8-12 member ring openings, and particularly ZSM-5 zeolite.
  • the material may be in the form of granules, pellets, monoliths, powders that are collected on filters, or combinations thereof.
  • a treated gaseous product stream is withdrawn from the adsorption zone and contains less than about 20 weight %, preferably less than about 10 weight %, and more preferably less that about 5 weight % of the heavy metal in the gaseous feed stream.
  • the heavy metal compound removal system may be contained in a separate downstream vessel from the vanadium oxide sorbent, or can be situated along with the vanadium oxide sorbent in a multiple stage contacting vessel so that the flue gas first contacts the vanadium oxide sorbent followed by the heavy metal compound removal sorbent.
  • the heavy metal compound removal system preferably results in the sorption of at least about 80% by weight of the heavy metal containing compounds that break through the vanadium oxide sorbent material, more preferably at least about 90% by weight, and most preferably at least about 95% by weight.
  • the overall sorptive efficiency may be affected by the presence of NO x and SO x compounds present in the flue gas.
  • SO 2 contained in the flue gas stream may be oxidized to SO 3 and then converted to H 2 SO 4 in the presence of water.
  • the H 2 SO 4 then may fill the pores of the vanadium oxide sorbent thereby decreasing the sorptive capacity thereof and blocking active catalyst sites. Therefore, it is preferable to employ an upstream NO x and SO x removal process in order to avoid fouling of the vanadium oxide sorbent material. Any conventional NO x and SO x removal process would be suitable for use with the present invention.
  • the NO x and SO x removal process should preferably remove at least about 50% by weight of all NO x and SO x present in the flue gas stream. It is preferable for the flue gas stream immediately prior to contact with the vanadium oxide sorbent to comprise less than about 400 ppm NO x , more preferably less than about 250 ppm, and most preferably less than about 150 ppm. Likewise, it is preferable for the flue gas stream immediately prior to contact with the vanadium oxide sorbent to comprise less than about 800 ppm SO x , more preferably less than about 500 ppm, and most preferably less than about 400 ppm.
  • the heavy metal compound removal system is capable of performing effectively even at high flue gas flow rates (i.e., greater than 10,000 gas hourly space velocity).
  • the sorbent material used in the heavy metal compound removal system may be placed in a fluidized or packed bed vessel, however, as with the vanadium oxide sorbent material system above, the pressure drop of the flue gas stream should be minimized to avoid requiring the use of additional equipment to compensate for the pressure drop.
  • the material was then tested for efficacy in removing elemental mercury entrained in an air stream at a concentration of approximately 1000 ⁇ g/m 3 (ppb w/v).
  • Approximately 0.97 g of the sorbent was placed in a fixed bed reactor, the temperature of which was held constant at 300° F.
  • the air flow rate through the fixed bed reactor was fixed at a gas hourly space velocity of >10,000 (approximately 200 mL/min).
  • the air stream entering and exiting the fixed bed reactor was periodically analyzed using a Jerome Mercury Analyzer.
  • FIG. 1 shows the mercury uptake versus the mercury breakthrough of the sorbent material.
  • literature data for sulfur impregnated activated charcoal (SIAC) a conventional sorbent for this application, is also shown.
  • the lithium promoted V 2 O 5 sorbent demonstrated excellent capacity for sequestering mercury when compared with the SIAC literature data.
  • FIG. 2 further demonstrates the effectiveness of the sorbent in removing mercury from the air stream in terms of efficiency of the sorbent versus mercury uptake. The sorbent exhibited greater than 95% efficiency over extended test periods. In sum, the test results indicate that the lithium promoted V 2 O 5 sorbent material has a high capacity for sorbing mercury and is exceptionally efficient in mercury removal.

Abstract

A composition comprising a vanadium oxide compound and an alkali metal promoter loaded onto a porous support material is disclosed. Methods of making and using the composition to remove heavy metals or heavy metal containing compounds from a fluid stream are also provided. Such methods are particularly useful in the removal of mercury and mercury compounds from flue gas streams produced from the combustion of hydrocarbon-containing materials such as coal and petroleum fuels.

Description

  • The invention relates to a composition and method for removing heavy metal contaminates from fluid streams. In one aspect, the invention relates to a method of preparing such composition. In yet another aspect, the invention relates to a process for removing heavy metal contaminates, such as mercury and mercury compounds, from flue gas streams produced from the combustion of hydrocarbon-containing materials.
    • BACKGROUND OF THE INVENTION
  • Heavy metals are released during the combustion process of many fossil fuels and/or waste materials. These heavy metals include, for example, arsenic, beryllium, lead, cadmium, chromium, nickel, zinc, mercury, and barium. Most of these heavy metals are toxic to humans and animals. In particular, elemental mercury and mercury compounds such as mercury chlorides are thought to compromise the health and mental acuity of young children and fetuses.
  • Furthermore, there is every indication that the amount of mercury, and possibly of other heavy metals, now legally allowed to be released by those combusting various fossil fuels and/or waste materials, including coal burning powerplants and petroleum refineries, will be reduced by future legislation. While a variety of adsorbents are available for capture of heavy metals (in particular mercury), these adsorbents tend to have low capacities and are easily deactivated by other components in the gas stream, such as sulfur oxides. Thus, there exists a need for a material that removes elemental mercury from gas streams and has a high capacity for retaining mercury as a nonvolatile compound.
    • SUMMARY OF THE INVENTION
  • It is an object of the present invention to provide an improved vanadium material with a high capacity for sorbing heavy metals and heavy metal compounds.
  • A further object of this invention is to provide a method for making an improved vanadium material by incorporating a vanadium oxide compound and an alkali metal hydroxide promoter with a porous support material.
  • Another object of this invention is to provide a process for removing heavy metals or heavy metal compounds from a fluid stream by contacting the fluid stream with an improved vanadium material.
  • Yet another object of this invention is to provide an improved vanadium material which when used in the removal of heavy metals results in the oxidation of the heavy metal to an oxidation state greater than zero.
  • It should be understood that the above-listed objects are only exemplary, and not all the objects listed above need be accomplished by the invention described and claimed herein.
  • In accordance with a first embodiment of the invention, the inventive composition comprises a porous support material including a vanadium oxide compound and an alkali metal vanadate incorporated thereon, therein, or thereon and therein.
  • In accordance with a second embodiment of the invention, the inventive composition comprises a porous support material impregnated with a vanadium oxide compound and an alkali metal promoter selected from the group consisting of lithium hydroxide, lithium vanadate, and mixtures thereof.
  • In accordance with a third embodiment of the invention, the inventive composition can be prepared by the method of: (a) mixing a vanadium oxide compound and an alkali metal hydroxide promoter with at least one porous support material.
  • In accordance with a fourth embodiment of the invention, the inventive composition can be used in the removal of at least one heavy metal or heavy metal containing compound from a fluid stream by (a) contacting the fluid stream with a porous support material having incorporated onto, into, or onto and into a vanadium oxide compound and an alkali metal promoter for sorption of at least a portion of the at least one heavy metal or heavy metal containing compound.
  • In accordance with a fifth embodiment of the invention, the inventive composition can be used in the removal of at least one heavy metal or heavy metal containing compound from a flue gas stream produced by the combustion of a hydrocarbon-containing fuel by: (a) contacting the flue gas stream with a first sorbent material comprising a porous support having incorporated onto, into, or onto and into a vanadium oxide compound and an alkali metal promoter for sorbing at least a portion of the at least one heavy metal or heavy metal containing compound present in the flue gas stream; and (b) contacting the flue gas with a second sorbent material different from the first sorbent material for sorbing at least a portion of the at least one heavy metal-containing compound not sorbed during step (a).
  • Other objects and advantages of the invention will become apparent from the detailed description and the appended claims.
    • BRIEF DESCRIPTION OF THE FIGURES
  • A preferred embodiment of the present invention is described in detail below with reference to the attached figures, wherein:
  • FIG. 1 is a graph of mercury uptake versus mercury breakthrough for a lithium promoted V2O5 sorbent on a porous support compared to a conventional activated charcoal sorbent; and
  • FIG. 2 is a graph of the mercury removal efficiency for a lithium promoted V2O5 sorbent on a porous support.
    • DETAILED DESCRIPTION OF THE INVENTION
  • Compositions according to the present invention generally comprise a porous support material with a vanadium oxide compound and an alkali metal promoter incorporated thereon, therein, or thereon and therein. Preferably, the vanadium oxide compound comprises V2O5, a hydrate of V2O5, a peroxo complex of vanadium oxide or combinations thereof. However, it is within the scope of the invention for the vanadium component to have any oxidation state greater than zero.
  • An alkali metal promoter is employed to increase the effectiveness of the vanadium oxide in sorbing heavy metals. Preferably, the alkali metal promoter is an alkali metal hydroxide such as lithium hydroxide. As discussed below, during formation of the inventive compositions, it is possible for at least a portion of the alkali metal hydroxide promoter to react with at least a portion of the vanadium oxide compound to form an alkali metal vanadate such as lithium vanadate. Hydrates of alkali metal hydroxides can also be used such as lithium hydroxide monohydrate. However, it is within the scope of the present invention for the promoter to be an elemental alkali metal, an alkali metal compound, or an ionic alkali metal species. Unless otherwise specified, the term “promoter” refers to any such alkali metal composition whether it was originally added to the inventive sorbent or whether it was formed in situ.
  • The vanadium oxide compound and promoter are loaded onto a porous support material. Preferably, the support material is selected from the group consisting of amorphous silica-alumina, a zeolite, a material comprising meta-kaolin, alumina, expanded perlite, and combinations thereof. It is most preferable to employ a silica-alumina support material such as meta-kaolin in conjunction with expanded perlite, however, it is possible that the support may comprise pure alumina or calcined alumina.
  • The porous support material generally comprises at least about 50% by weight of the total composition, preferably between about 50-99% by weight, more preferably between about 75-95% by weight, and most preferably between about 80-90% by weight. In order to maximize the sorptive capacity of the composition, the support material preferably has a surface area of at least about 75 m2/g, more preferably at least about 100 m2/g, and most preferably at least about 150 m2/g.
  • The overall composition preferably comprises from about 0.5-40% by weight vanadium. Unless otherwise specified, the phrase “by weight vanadium” is defined as the elemental weight of vanadium present in the composition. More preferably, the composition comprises from about 1-35% by weight vanadium, and most preferably from about 2-25% by weight.
  • The composition preferably comprises from about 0.5-50% by weight of the alkali metal promoter, more preferably from about 1-30% by weight, and most preferably from about 5-25% by weight. The weight ratio of vanadium oxide to promoter is preferably within the range of about 10:1 to 1:10, more preferably between about 5:1 to 1:5, and most preferably between about 4:1 to 1:1.
  • The sorbent material is formed by mixing a vanadium oxide compound and an alkali metal promoter with at least one porous support. The vanadium oxide compound and promoter should be intimately contacted with the support so that the vanadium oxide compound and promoter become incorporated onto, into, or onto and into the support.
  • One avenue for accomplishing this intimate mixing is to dispense the vanadium oxide and promoter in a first solution. Water is a preferred solvent for forming this solution, however, any solvent capable of dissolving both the vanadium oxide and promoter may be used. When dispersed in an aqueous solution, the vanadium oxide comprises from about 0.5-70% by weight of the solution, more preferably between about 5-60% by weight, and most preferably from about 10-50% by weight. Similarly, when dispersed in an aqueous solution, the promoter comprises from about 0.05-50% by weight of the solution, more preferably from about 0.5-40% by weight, and most preferably from about 1-30% by weight. At the same time, the porous support is dispersed in a second solution, with water being a preferred solvent.
  • If an alkali metal hydroxide is selected as the promoter that is mixed with the vanadium oxide compound, generally, at least a portion of the alkali metal hydroxide reacts with at least a portion of the vanadium oxide compound to form an alkali metal vanadate, also referred to herein as a “promoter.”
  • The first and second solutions are then mixed together thereby loading the vanadium oxide and promoter onto, into, or onto and into the support. The mixture is then dried, and preferably, the resulting sorbent material is in a granular or powder form. It is possible that the porous support used is not in a finely divided form prior to mixing with the vanadium oxide and promoter solution. If such is the case, it is preferable to crush and sieve the dried sorbent material to an acceptable particle size for a given application. The sorbant material may also be pelletized, formed into monoliths, or incorporated into a foam in order to render it suitable for a specific application.
  • The inventive sorbent material is particularly useful in the removal of heavy metals and heavy metal containing compounds from fluid streams, especially flue gas streams produced by the combustion of hydrocarbon-containing materials such as coal and petroleum fuels. As noted above, such fluid streams are often contaminated with at least one heavy metal or compound containing a heavy metal selected from the group consisting of arsenic, beryllium, lead, cadmium, chromium, nickel, zinc, mercury, and barium. In one aspect, methods of removing heavy metal and heavy metal containing compounds from fluid streams comprise providing a sorbent composition according to the present invention and contacting the stream with the inventive sorbent.
  • Flue gas, such as that created by the combustion of hydrocarbon-containing compounds, generally comprises at least about 10% by weight N2, more preferably at least about 50% by weight, and most preferably between about 75-90% by weight. Flue gas also generally comprises less than about 10% by weight of uncombusted hydrocarbons, more preferably less than about 5% by weight, and most preferably less than about 1% by weight. As described below, in a particularly preferred application, the flue gas will have already been treated for removal of NOx and SOx prior to any heavy metal removal process as the presence of high levels of NOx and SOx compounds may lead to fouling of the heavy metal removal sorbents. Generally, the flue gas comprises less than about 800 ppm of SOx compounds such as SO2, more preferably less than about 500 ppm, and most preferably less than about 400 ppm. Also, the flue gas preferably comprises less than about 400 ppm NOx such as NO and NO2, more preferably less than about 250 ppm, and most preferably less than about 150 ppm. Flue gas may also comprise between about 2.5-10% by weight O2, between about 1-5% by weight CO2, and between about 5-20% by weight H2O.
  • Preferably, the pressure drop associated with the contacting step should not exceed more than about 20 psia. More preferably, the pressure drop in the fluid stream is less than about 10 psia, and most preferably less than about 5 psia. Typically, flue gas streams do not flow under high pressures. Therefore, if the pressure drop is too great, back pressure is created and can affect the combustion process by which the flue gas is created. The arrangement of the sorbent material in the vessel in which contacting occurs can assist in minimizing this pressure drop. Preferably, the sorbent material comprises finely divided particles that are suspended in the fluid stream during the contacting step. Alternatively, the sorbent material may be positioned in a fluidized bed, placed in a packed bed column, formed into monoliths, or incorporated into a foam. With the latter arrangements, pressure drop may become much more of a concern and may require the use of fans or other equipment to increase the pressure of the flue gas stream.
  • The fluid stream containing the heavy metal contaminant preferably has a temperature of between about 50-400° F. during the contacting step, more preferably between about 100-375° F., and most preferably between about 200-350° F. The temperature of the fluid stream at the contacting stage is in part affected by upstream processes such as particulate removal systems (i.e., cyclones), other contaminant removal systems, heat exchange systems, etc. The contacting step results in the sorption of at least about 80% by weight of the heavy metals contained in the fluid stream, more preferably at least about 90% by weight, even more preferably at least about 95% by weight, and most preferably at least about 98% by weight. As previously stated, the vanadium oxide incorporated support material exhibits a high capacity for sorbing heavy metals and heavy metal containing compounds. Preferably, the vanadium oxide material is capable of sorbing at least about 1 atom of a heavy metal per every 5 atoms of vanadium. More preferably, the ratio of heavy metal atoms sorbed to vanadium atoms is at least about 1:3, and most preferably 1:1.
  • The sorbent material also exhibits the ability to oxidize the elemental heavy metal into a heavy metal containing compound such as a heavy metal oxide or chloride. Using mercury as an example, the sorbent material oxidizes mercury into various oxidized species such as Hg+1, Hg+2, or mercury compounds such as HgO, HgCl, and HgCl2. At times, due to system inefficiencies or sorbent saturation, some of these heavy metal containing compounds may desorb or break free from the sorbent material. In that case, it can be particularly useful to employ a downstream heavy metal compound removal system in conjunction with the above-described sorbent system. In the heavy metal compound removal system, the gaseous product stream is contacted with a separate adsorbent in an adsorption zone. The adsorbent can be any adsorbent capable of adsorbing a heavy metal; however, preferred materials for removing the heavy metal compounds include those having a hydrophobic surface with pore openings of less than about 10 Å, and high pore volumes. More preferably, the adsorbent comprises, consists of or consists essentially of a material selected from the group consisting of a zeolite, amorphous carbon and combinations thereof. The amorphous carbon can be an activated carbon and/or activated charcoal. Exemplary zeolites include those with 8-12 member ring openings, and particularly ZSM-5 zeolite. Furthermore, the material may be in the form of granules, pellets, monoliths, powders that are collected on filters, or combinations thereof. A treated gaseous product stream is withdrawn from the adsorption zone and contains less than about 20 weight %, preferably less than about 10 weight %, and more preferably less that about 5 weight % of the heavy metal in the gaseous feed stream.
  • The heavy metal compound removal system may be contained in a separate downstream vessel from the vanadium oxide sorbent, or can be situated along with the vanadium oxide sorbent in a multiple stage contacting vessel so that the flue gas first contacts the vanadium oxide sorbent followed by the heavy metal compound removal sorbent.
  • While the vanadium oxide sorbent material exhibits a relatively high capacity for sorbing heavy metals and heavy metal containing compounds, its cost is relatively higher than the cost for conventional heavy metal compound sorbent materials such as zeolite. Therefore, from an economic standpoint, it may be desirable to employ a relatively small amount of the vanadium oxide sorbent compared to the conventional sorbent material. Once the sorptive capacity of the vanadium oxide sorbent has sufficiently diminished, it will not be able to sorb sufficient quantities of the heavy metal containing compounds formed by the catalytic action of the vanadium oxide sorbent. These heavy metal containing compounds may then be sorbed by the lesser expensive heavy metal compound sorbent material located downstream from the vanadium oxide sorbent.
  • The heavy metal compound removal system preferably results in the sorption of at least about 80% by weight of the heavy metal containing compounds that break through the vanadium oxide sorbent material, more preferably at least about 90% by weight, and most preferably at least about 95% by weight.
  • In addition to the vanadium oxide sorbent material becoming saturated, the overall sorptive efficiency may be affected by the presence of NOx and SOx compounds present in the flue gas. For example, SO2 contained in the flue gas stream may be oxidized to SO3 and then converted to H2SO4 in the presence of water. The H2SO4 then may fill the pores of the vanadium oxide sorbent thereby decreasing the sorptive capacity thereof and blocking active catalyst sites. Therefore, it is preferable to employ an upstream NOx and SOx removal process in order to avoid fouling of the vanadium oxide sorbent material. Any conventional NOx and SOx removal process would be suitable for use with the present invention. The NOx and SOx removal process should preferably remove at least about 50% by weight of all NOx and SOx present in the flue gas stream. It is preferable for the flue gas stream immediately prior to contact with the vanadium oxide sorbent to comprise less than about 400 ppm NOx, more preferably less than about 250 ppm, and most preferably less than about 150 ppm. Likewise, it is preferable for the flue gas stream immediately prior to contact with the vanadium oxide sorbent to comprise less than about 800 ppm SOx, more preferably less than about 500 ppm, and most preferably less than about 400 ppm.
  • The heavy metal compound removal system is capable of performing effectively even at high flue gas flow rates (i.e., greater than 10,000 gas hourly space velocity). The sorbent material used in the heavy metal compound removal system may be placed in a fluidized or packed bed vessel, however, as with the vanadium oxide sorbent material system above, the pressure drop of the flue gas stream should be minimized to avoid requiring the use of additional equipment to compensate for the pressure drop.
    • EXAMPLE
  • The following example illustrates preferred sorbent materials and methods of making the same in accordance with the present invention. This example should not be taken as limiting the scope of the present invention in any way.
  • In this example, a sorbent material according to the present invention was prepared by forming a solution comprising 17.816 g of LiOH.H2O and 77.229 g of V2O5 dissolved in 60 g of deionized water. A separate dispersion was prepared containing 60 g of deionized water, 30 g of alumina (DISPAL), 60 g of expanded perlite, and 20 g of calcined Kaolin or more generally calcined clay, or more specifically meta Kaolin. The solution and dispersion were mixed together forming a thick, paste-like material. This material was extruded through a ⅛ inch die and dried overnight at 248° F. The next day, the extrudate was crushed so as to form a granular material that could be passed through a 20-40 mesh sieve.
  • The material was then tested for efficacy in removing elemental mercury entrained in an air stream at a concentration of approximately 1000 μg/m3 (ppb w/v). Approximately 0.97 g of the sorbent was placed in a fixed bed reactor, the temperature of which was held constant at 300° F. The air flow rate through the fixed bed reactor was fixed at a gas hourly space velocity of >10,000 (approximately 200 mL/min). The air stream entering and exiting the fixed bed reactor was periodically analyzed using a Jerome Mercury Analyzer.
  • FIG. 1 shows the mercury uptake versus the mercury breakthrough of the sorbent material. For purposes of comparison, literature data for sulfur impregnated activated charcoal (SIAC), a conventional sorbent for this application, is also shown. The lithium promoted V2O5 sorbent demonstrated excellent capacity for sequestering mercury when compared with the SIAC literature data. FIG. 2 further demonstrates the effectiveness of the sorbent in removing mercury from the air stream in terms of efficiency of the sorbent versus mercury uptake. The sorbent exhibited greater than 95% efficiency over extended test periods. In sum, the test results indicate that the lithium promoted V2O5 sorbent material has a high capacity for sorbing mercury and is exceptionally efficient in mercury removal.

Claims (55)

1. A composition comprising a porous support material including a vanadium oxide compound and an alkali metal vanadate incorporated thereon, therein, or thereon and therein.
2. A composition in accordance with claim 1 wherein said vanadium oxide compound comprises V2O5, a hydrate of V2O5, a peroxo complex of vanadium oxide, or mixtures thereof.
3. A composition in accordance with claim 1 wherein said alkali metal vanadate is lithium vanadate.
4. A composition in accordance with claim 1 wherein said porous support material is selected from the group consisting of amorphous silica-alumina, a zeolite, a material comprising meta-kaolin, alumina, expanded perlite, and combinations thereof.
5. A composition in accordance with claim 1 wherein said porous support material comprises at least about 50% by weight of the total weight of said composition.
6. A composition in accordance with claim 1 wherein said composition comprises from about 0.5-40% by weight vanadium.
7. A composition in accordance with claim 1 wherein said porous support material has a surface area of at least about 75 m2/g.
8. A composition in accordance with claim 1 wherein said composition comprises from about 0.5-50% by weight of said alkali metal vanadate.
9. A composition in accordance with claim 1 wherein the weight ratio of vanadium oxide to alkali metal vanadate is from about 10:1 to 1:10.
10. A composition in accordance with claim 1 wherein said composition further comprises a quantity of an alkali metal hydroxide.
11. A composition in accordance with claim 10 wherein said alkali metal hydroxide is lithium hydroxide.
12. A porous sorbent composition comprising a porous support material impregnated with a vanadium oxide compound and an alkali metal promoter selected from the group consisting of lithium hydroxide, lithium vanadate, and mixtures thereof.
13. A composition in accordance with claim 12 wherein said vanadium oxide compound comprises V2O5, a hydrate of V2O5, a peroxo complex of vanadium oxide, or mixtures thereof.
14. A composition in accordance with claim 12 wherein said porous support material is selected from the group consisting of amorphous silica-alumina, a zeolite, a material comprising meta-kaolin, alumina, expanded perlite, and combinations thereof.
15. A composition in accordance with claim 12 wherein said porous support material comprises at least about 50% by weight of the total weight of said composition.
16. A composition in accordance with claim 12 wherein said composition comprises from about 0.5-40% by weight vanadium.
17. A composition in accordance with claim 12 wherein said porous support material has a surface area of at least about 75 m2/g.
18. A composition in accordance with claim 12 wherein said composition comprises from about 0.5-50% by weight of said alkali metal promoter.
19. A composition in accordance with claim 12 wherein the weight ratio of vanadium oxide to alkali metal hydroxide is from about 10:1 to 1:10.
20. A method for forming a sorbent material comprising:
(a) mixing a vanadium oxide compound and an alkali metal hydroxide promoter with at least one porous support material.
21. A method in accordance with claim 20 wherein said method further comprises:
(b) dispersing said vanadium oxide and said promoter in a first aqueous solution prior to step (a).
22. A method in accordance with claim 21 wherein said first aqueous solution comprises from about 0.5-70% by weight of said vanadium oxide compound and from about 0.05-50% by weight of said promoter.
23. A method in accordance with claim 21 wherein said method further comprises:
(c) dispersing said porous support components in a second aqueous solution prior to step (a).
24. A method in accordance with claim 20 wherein said promoter is lithium hydroxide.
25. A method in accordance with claim 20 wherein said at least one porous support material is selected from the group consisting of amorphous silica-alumina, a zeolite, a material comprising meta-kaolin, alumina, expanded perlite, and combinations thereof.
26. A method in accordance with claim 20 wherein at least a portion of said alkali metal hydroxide promoter reacts with at least a portion of said vanadium oxide compound to form an alkali metal vanadate.
27. A method of removing at least one heavy metal or heavy metal containing compound from a fluid stream, said method comprising the step of:
(a) contacting said fluid stream with a porous support material having incorporated onto, into, or onto and into a vanadium oxide compound and an alkali metal promoter for sorption of at least a portion of said at least one heavy metal or heavy metal containing compound.
28. A method in accordance with claim 27 wherein said vanadium oxide incorporated support material oxidizes said heavy metal into an oxidized heavy metal species or heavy metal containing compound.
29. A method in accordance with claim 27 wherein said porous support material is selected from the group consisting of amorphous silica-alumina, a zeolite, a material comprising meta-kaolin, alumina, expanded perlite, and combinations thereof.
30. A method in accordance with claim 27 wherein said vanadium oxide compound comprises V2O5, a hydrate of V2O5, a peroxo complex of vanadium oxide, or mixtures thereof.
31. A method in accordance with claim 27 wherein said promoter is selected from the group consisting of lithium vanadate, lithium hydroxide, and mixtures thereof.
32. A method in accordance with claim 27 wherein said contacting step results in a pressure drop in said fluid stream of less than about 20 psia.
33. A method in accordance with claim 32 wherein said contacting step results in a pressure drop in said fluid stream of less than about 10 psia.
34. A method in accordance with claim 27 wherein said fluid stream has a temperature between about 50-400° F. during said contacting step.
35. A method in accordance with claim 27 wherein said fluid stream comprises at least one heavy metal or compound containing a heavy metal selected from the group consisting of arsenic, beryllium, lead, cadmium, chromium, nickel, zinc, mercury, and barium.
36. A method in accordance with claim 35 wherein said at least one heavy metal is mercury.
37. A method in accordance with claim 27 wherein said vanadium oxide incorporated support material comprises finely divided particles that are suspended in said fluid stream during said contacting step, pelletized particles placed in a fixed or fluidized bed, monoliths, or combinations thereof.
38. A method in accordance with claim 27 wherein said contacting step results in the sorption of at least about 80% by weight of the at least one heavy metal or heavy metal containing compound contained in said fluid stream.
39. A method in accordance with claim 27 wherein said vanadium oxide incorporated support material is capable of sorbing at least about 1 atom of said heavy metal per every 5 atoms of vanadium.
40. A process for the removal of at least one heavy metal or heavy metal containing compound from a flue gas stream produced by the combustion of a hydrocarbon-containing fuel comprising the steps of:
(a) contacting said flue gas stream with a first sorbent material comprising a porous support having incorporated onto, into, or onto and into a vanadium oxide compound and an alkali metal promoter for sorbing at least a portion of said at least one heavy metal or heavy metal containing compound present in said flue gas stream; and
(b) contacting said flue gas with a second sorbent material different from said first sorbent material for sorbing at least a portion of said at least one heavy metal-containing compound not sorbed during step (a).
41. A process as recited in claim 40 wherein said second sorbent material comprises a material selected from the group consisting of porous zeolite materials, amorphous carbons, and combinations thereof.
42. A process as recited in claim 41 wherein said amorphous carbons are selected from the group consisting of activated charcoal, activated carbon, and combinations thereof.
43. A process as recited in claim 41 wherein said porous zeolite material comprises ZSM-5 zeolite.
44. A process as recited in claim 40 wherein said flue gas stream comprises at least one heavy metal or compound containing a heavy metal selected from the group consisting of arsenic, beryllium, lead, cadmium, chromium, nickel, zinc, mercury, and barium.
45. A process as recited in claim 44 wherein said at least one heavy metal is mercury.
46. A process as recited in claim 40 wherein said vanadium oxide compound comprises V2O5, a hydrate of V2O5, a peroxo complex of vanadium oxide, or combinations thereof.
47. A process as recited in claim 40 wherein step (a) results in a pressure drop in said flue gas stream of less than about 20 psia.
48. A process as recited in claim 40 wherein said flue gas stream has a temperature between about 50-400° F. during step (a).
49. A process as recited in claim 40 wherein said vanadium oxide incorporated support material comprises finely divided particles that are suspended in said flue gas stream during step (a), pelletized particles placed in a fixed or fluidized bed, monoliths, or combinations thereof.
50. A process as recited in claim 40 wherein step (a) results in the sorption of at least about 80% by weight of said at least one heavy metal or heavy metal containing compound contained in said flue gas stream.
51. A process as recited in claim 40 wherein step (b) results in the removal of at least about 80% by weight of said at least one heavy metal compound from the flue gas stream leaving step (a).
52. A process as recited in claim 40 wherein said alkali metal promoter is selected from the group consisting of lithium vanadate, lithium hydroxide, and mixtures thereof.
53. A process as recited in claim 40 wherein prior to step (a) said process includes removal of at least about 50% by weight of all NOx and SOx present in said flue gas.
54. A process as recited in claim 40 wherein said flue gas stream comprises less than about 400 ppm NOx and less than about 800 ppm SOx immediately prior to step (a).
55. A process as recited in claim 40 wherein said vanadium oxide incorporated support material oxidizes said heavy metal into an oxidized heavy metal species or heavy metal containing compound during step (a).
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249495A1 (en) * 2006-03-15 2007-10-25 Xingtao Gao Catalyst composition for reducing gasoline sulfur content in catalytic cracking process
CN100431957C (en) * 2006-09-12 2008-11-12 内蒙古蒙西高岭粉体股份有限公司 Technique of fluidized instant calcinations of kaolin in coal series
WO2011116788A1 (en) 2010-03-25 2011-09-29 Saint Petersburg State University Layered titanates
CN102437322A (en) * 2011-11-23 2012-05-02 陕西科技大学 Method for preparing LiV3O8 microcrystalline through microwave and self-propagation combustion
CN114177880A (en) * 2021-12-23 2022-03-15 安徽建筑大学 Application of sodium vanadate hydrate film as heavy metal adsorption material

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8489231B2 (en) * 2009-09-18 2013-07-16 Raf Technology, Inc. Loop mail processing
US8404026B2 (en) * 2010-07-21 2013-03-26 Corning Incorporated Flow-through substrates and methods for making and using them
US8673133B2 (en) 2010-09-16 2014-03-18 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8663460B2 (en) 2010-09-16 2014-03-04 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8728304B2 (en) 2010-09-16 2014-05-20 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8702975B2 (en) 2010-09-16 2014-04-22 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8728303B2 (en) 2010-11-19 2014-05-20 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8721874B2 (en) 2010-11-19 2014-05-13 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
US8721873B2 (en) 2010-11-19 2014-05-13 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
CN102353399A (en) * 2011-07-05 2012-02-15 上海电力学院 Conversion system for flue gas in flue of coal-fired boiler and simulation method thereof
US9381492B2 (en) * 2011-12-15 2016-07-05 Clariant Corporation Composition and process for mercury removal
CN102565287A (en) * 2012-01-05 2012-07-11 上海电力学院 Evaluation device for coal-fired flue gas pollutant sorbent and application thereof
EP2850153A4 (en) 2012-05-16 2016-03-09 Chevron Usa Inc Process, method, and system for removing heavy metals from fluids
US9447674B2 (en) 2012-05-16 2016-09-20 Chevron U.S.A. Inc. In-situ method and system for removing heavy metals from produced fluids
CA2872792C (en) 2012-05-16 2020-08-25 Chevron U.S.A. Inc. Process, method, and system for removing mercury from fluids
AU2013262687B2 (en) 2012-05-16 2018-02-08 Chevron U.S.A. Inc. Process, method, and system for removing mercury from fluids
US9370757B2 (en) 2012-08-21 2016-06-21 Uop Llc Pyrolytic reactor
US9327265B2 (en) 2012-08-21 2016-05-03 Uop Llc Production of aromatics from a methane conversion process
US9656229B2 (en) 2012-08-21 2017-05-23 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US20140058096A1 (en) * 2012-08-21 2014-02-27 Uop Llc Heavy metals removal and methane conversion process using a supersonic flow reactor
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US9205398B2 (en) 2012-08-21 2015-12-08 Uop Llc Production of butanediol from a methane conversion process
US8937186B2 (en) 2012-08-21 2015-01-20 Uop Llc Acids removal and methane conversion process using a supersonic flow reactor
US9707530B2 (en) 2012-08-21 2017-07-18 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US9308513B2 (en) 2012-08-21 2016-04-12 Uop Llc Production of vinyl chloride from a methane conversion process
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US9434663B2 (en) 2012-08-21 2016-09-06 Uop Llc Glycols removal and methane conversion process using a supersonic flow reactor
US9689615B2 (en) 2012-08-21 2017-06-27 Uop Llc Steady state high temperature reactor
US9023255B2 (en) 2012-08-21 2015-05-05 Uop Llc Production of nitrogen compounds from a methane conversion process
US9234141B2 (en) 2013-03-14 2016-01-12 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from oily solids
US9169445B2 (en) 2013-03-14 2015-10-27 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from oily solids
US9023196B2 (en) 2013-03-14 2015-05-05 Chevron U.S.A. Inc. Process, method, and system for removing heavy metals from fluids
CN111569599B (en) * 2019-11-08 2021-12-10 杭州超钜科技有限公司 Composite fiber type mercury capturing device and preparation method of mercury capturing composite fiber

Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2178602A (en) * 1937-11-30 1939-11-07 Universal Oil Prod Co Manufacture of diolefins
US2824880A (en) * 1953-04-10 1958-02-25 Ciba Ltd Process for the manufacture of anthraquinone from anthracene by catalytic oxidation
US2985515A (en) * 1958-03-05 1961-05-23 Union Carbide Corp Fluidized solids contacting system
US3472612A (en) * 1967-09-11 1969-10-14 Nat Lead Co Process for recovering vanadium from an alkali metal vanadate solution
US3501897A (en) * 1966-11-28 1970-03-24 Shell Oil Co Process for removing sulfur oxides from gas mixtures
US3615196A (en) * 1969-05-05 1971-10-26 Exxon Research Engineering Co Process for the purification of flue gas
US3655585A (en) * 1969-08-28 1972-04-11 Mallory & Co Inc P R Method of preparing cathodic electrodes
US4001376A (en) * 1972-12-15 1977-01-04 Exxon Research And Engineering Company Flue gas desulfurization sorbent and process
USRE29145E (en) * 1969-05-23 1977-03-01 Bayer Aktiengesellschaft Catalyst for sulfuric acid contact process
US4039478A (en) * 1972-12-15 1977-08-02 Exxon Research And Engineering Company Flue gas desulfurization sorbent
US4059418A (en) * 1973-08-23 1977-11-22 Exxon Research & Engineering Co. Flue gas desulfurization sorbent and process
US4085195A (en) * 1971-11-01 1978-04-18 Exxon Research & Engineering Co. Sorbent preparation and process using same
US4092271A (en) * 1976-09-27 1978-05-30 The Lummus Company Supported vanadia catalyst for nitrile production and process for preparing the catalyst
US4101631A (en) * 1976-11-03 1978-07-18 Union Carbide Corporation Selective adsorption of mercury from gas streams
US4184546A (en) * 1976-09-28 1980-01-22 Schlumberger Technology Corporation Anchoring apparatus for tools used in determining the stuck point of a conduit in a borehole
US4193894A (en) * 1979-01-11 1980-03-18 Monsanto Company Catalyst for oxidation of sulfur dioxide
US4274941A (en) * 1974-10-10 1981-06-23 Bergwerksverband Gmbh Process for generating combustible gases, liquid coal byproducts and superheated steam from coal
US4284781A (en) * 1977-07-28 1981-08-18 The Lummus Company Supported vanadia catalyst and use thereof for nitrile production
US4474896A (en) * 1983-03-31 1984-10-02 Union Carbide Corporation Adsorbent compositions
US4596752A (en) * 1983-11-07 1986-06-24 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Electrochemical cell structures and materials therefor
US4781902A (en) * 1986-10-29 1988-11-01 Haldor Topsoe A/S Process for the removal of nitrogen oxides and sulphur oxides from flue gases
US4874525A (en) * 1988-10-26 1989-10-17 Uop Purification of fluid streams containing mercury
US5039582A (en) * 1989-04-12 1991-08-13 Consiglio Nazionale Delle Ricerche High energy and high power lithium storage batteries, and method for producing the same
US5223145A (en) * 1992-10-09 1993-06-29 Uop Removal of mercury from process streams
US5313913A (en) * 1993-05-28 1994-05-24 Ebara Corporation Pressurized internal circulating fluidized-bed boiler
US5354357A (en) * 1993-03-01 1994-10-11 Uop Removal of mercury from process streams
US5409522A (en) * 1994-04-20 1995-04-25 Ada Technologies, Inc. Mercury removal apparatus and method
US5513599A (en) * 1993-03-03 1996-05-07 Ebara Corporation Pressurized internal circulating fluidized-bed boiler
US5569436A (en) * 1993-06-10 1996-10-29 Beco Engineering Company Removal of mercury and cadmium and their compounds from incinerator flue gases
US5576120A (en) * 1994-01-19 1996-11-19 Saidi M Yazid Solid secondary lithium cell based on Lix V5 O13 cathode material
US5607496A (en) * 1994-06-01 1997-03-04 Brooks Rand, Ltd. Removal of mercury from a combustion gas stream and apparatus
US5872323A (en) * 1997-08-01 1999-02-16 Remington Arms Co., Inc. Gas operated firearm piston/piston seal assembly
US5922090A (en) * 1994-03-10 1999-07-13 Ebara Corporation Method and apparatus for treating wastes by gasification
US6027697A (en) * 1995-08-08 2000-02-22 Ebara Corporation Method and apparatus for treating combustion exhaust gases
US6136476A (en) * 1999-01-29 2000-10-24 Hydro-Quebec Corporation Methods for making lithium vanadium oxide electrode materials
US6136281A (en) * 1999-03-31 2000-10-24 Tennessee Valley Authority Method to control mercury emissions from exhaust gases
US6248217B1 (en) * 1997-04-10 2001-06-19 The University Of Cincinnati Process for the enhanced capture of heavy metal emissions
US6613299B2 (en) * 2001-11-13 2003-09-02 Sud-Chemie Prototech, Inc. Catalyzed diesel particulate matter exhaust filter

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4401572A (en) * 1979-11-15 1983-08-30 Mobil Oil Corporation Selective zeolite sorption of group V-B element hydrides and derivatives thereof
DE3232729A1 (en) * 1982-09-03 1984-03-08 Degussa Ag, 6000 Frankfurt METHOD FOR REDUCING THE IGNITION TEMPERATURE OF DIESEL CARBON FILTERED OUT OF THE EXHAUST GAS FROM DIESEL ENGINES
US5080799A (en) * 1990-05-23 1992-01-14 Mobil Oil Corporation Hg removal from wastewater by regenerative adsorption
US5096681A (en) * 1991-02-22 1992-03-17 Phillips Petroleum Company Removal of trialkyl arsine from fluids
US5281258A (en) * 1992-12-21 1994-01-25 Uop Removal of mercury impurity from natural gas
US5432141A (en) * 1994-03-15 1995-07-11 The Standard Oil Company Preparation of attrition resistant vanadium-antimony oxide catalysts
US5785932A (en) * 1996-02-22 1998-07-28 Environmental Elements Corp. Catalytic reactor for oxidizing mercury vapor
US6013599A (en) * 1998-07-15 2000-01-11 Redem Corporation Self-regenerating diesel exhaust particulate filter and material
US7048781B1 (en) * 2002-10-07 2006-05-23 Ada Technologies, Inc. Chemically-impregnated silicate agents for mercury control
US6719828B1 (en) * 2001-04-30 2004-04-13 John S. Lovell High capacity regenerable sorbent for removal of mercury from flue gas
JP4831801B2 (en) * 2001-08-09 2011-12-07 三菱重工業株式会社 Method and apparatus for removing mercury from exhaust gas
US7081434B2 (en) * 2001-11-27 2006-07-25 Sinha Rabindra K Chemical formulations for the removal of mercury and other pollutants present in fluid streams
US6919029B2 (en) * 2002-02-14 2005-07-19 Trustees Of Stevens Institute Of Technology Methods of preparing a surface-activated titanium oxide product and of using same in water treatment processes
KR20120065439A (en) * 2002-10-17 2012-06-20 엔테그리스, 아이엔씨. Method for purifying carbon dioxide
JP4175465B2 (en) * 2003-02-07 2008-11-05 三菱重工業株式会社 Method and system for removing mercury from exhaust gas
JP4395315B2 (en) * 2003-04-11 2010-01-06 三菱重工業株式会社 Method and system for removing mercury from exhaust gas
JP2004337781A (en) * 2003-05-16 2004-12-02 Mitsubishi Heavy Ind Ltd Exhaust gas treating method, exhaust gas treating system, and catalyst oxidation apparatus
TWI306410B (en) * 2003-10-22 2009-02-21 Nippon Catalytic Chem Ind Method for treating exhaust gas
US20050207955A1 (en) * 2004-03-17 2005-09-22 Bo Wang Mercury adsorbent composition, process of making same and method of separating mercury from fluids

Patent Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2178602A (en) * 1937-11-30 1939-11-07 Universal Oil Prod Co Manufacture of diolefins
US2824880A (en) * 1953-04-10 1958-02-25 Ciba Ltd Process for the manufacture of anthraquinone from anthracene by catalytic oxidation
US2985515A (en) * 1958-03-05 1961-05-23 Union Carbide Corp Fluidized solids contacting system
US3501897A (en) * 1966-11-28 1970-03-24 Shell Oil Co Process for removing sulfur oxides from gas mixtures
US3472612A (en) * 1967-09-11 1969-10-14 Nat Lead Co Process for recovering vanadium from an alkali metal vanadate solution
US3615196A (en) * 1969-05-05 1971-10-26 Exxon Research Engineering Co Process for the purification of flue gas
USRE29145E (en) * 1969-05-23 1977-03-01 Bayer Aktiengesellschaft Catalyst for sulfuric acid contact process
US3655585A (en) * 1969-08-28 1972-04-11 Mallory & Co Inc P R Method of preparing cathodic electrodes
US4085195A (en) * 1971-11-01 1978-04-18 Exxon Research & Engineering Co. Sorbent preparation and process using same
US4001376A (en) * 1972-12-15 1977-01-04 Exxon Research And Engineering Company Flue gas desulfurization sorbent and process
US4039478A (en) * 1972-12-15 1977-08-02 Exxon Research And Engineering Company Flue gas desulfurization sorbent
US4059418A (en) * 1973-08-23 1977-11-22 Exxon Research & Engineering Co. Flue gas desulfurization sorbent and process
US4274941A (en) * 1974-10-10 1981-06-23 Bergwerksverband Gmbh Process for generating combustible gases, liquid coal byproducts and superheated steam from coal
US4092271A (en) * 1976-09-27 1978-05-30 The Lummus Company Supported vanadia catalyst for nitrile production and process for preparing the catalyst
US4184546A (en) * 1976-09-28 1980-01-22 Schlumberger Technology Corporation Anchoring apparatus for tools used in determining the stuck point of a conduit in a borehole
US4101631A (en) * 1976-11-03 1978-07-18 Union Carbide Corporation Selective adsorption of mercury from gas streams
US4284781A (en) * 1977-07-28 1981-08-18 The Lummus Company Supported vanadia catalyst and use thereof for nitrile production
US4193894A (en) * 1979-01-11 1980-03-18 Monsanto Company Catalyst for oxidation of sulfur dioxide
US4474896A (en) * 1983-03-31 1984-10-02 Union Carbide Corporation Adsorbent compositions
US4596752A (en) * 1983-11-07 1986-06-24 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Electrochemical cell structures and materials therefor
US4781902A (en) * 1986-10-29 1988-11-01 Haldor Topsoe A/S Process for the removal of nitrogen oxides and sulphur oxides from flue gases
US4874525A (en) * 1988-10-26 1989-10-17 Uop Purification of fluid streams containing mercury
US5039582A (en) * 1989-04-12 1991-08-13 Consiglio Nazionale Delle Ricerche High energy and high power lithium storage batteries, and method for producing the same
US5223145A (en) * 1992-10-09 1993-06-29 Uop Removal of mercury from process streams
US5354357A (en) * 1993-03-01 1994-10-11 Uop Removal of mercury from process streams
US5513599A (en) * 1993-03-03 1996-05-07 Ebara Corporation Pressurized internal circulating fluidized-bed boiler
US5313913A (en) * 1993-05-28 1994-05-24 Ebara Corporation Pressurized internal circulating fluidized-bed boiler
US5569436A (en) * 1993-06-10 1996-10-29 Beco Engineering Company Removal of mercury and cadmium and their compounds from incinerator flue gases
US5576120A (en) * 1994-01-19 1996-11-19 Saidi M Yazid Solid secondary lithium cell based on Lix V5 O13 cathode material
US5922090A (en) * 1994-03-10 1999-07-13 Ebara Corporation Method and apparatus for treating wastes by gasification
US5409522A (en) * 1994-04-20 1995-04-25 Ada Technologies, Inc. Mercury removal apparatus and method
US5607496A (en) * 1994-06-01 1997-03-04 Brooks Rand, Ltd. Removal of mercury from a combustion gas stream and apparatus
US6027697A (en) * 1995-08-08 2000-02-22 Ebara Corporation Method and apparatus for treating combustion exhaust gases
US6248217B1 (en) * 1997-04-10 2001-06-19 The University Of Cincinnati Process for the enhanced capture of heavy metal emissions
US5872323A (en) * 1997-08-01 1999-02-16 Remington Arms Co., Inc. Gas operated firearm piston/piston seal assembly
US6136476A (en) * 1999-01-29 2000-10-24 Hydro-Quebec Corporation Methods for making lithium vanadium oxide electrode materials
US6136281A (en) * 1999-03-31 2000-10-24 Tennessee Valley Authority Method to control mercury emissions from exhaust gases
US6613299B2 (en) * 2001-11-13 2003-09-02 Sud-Chemie Prototech, Inc. Catalyzed diesel particulate matter exhaust filter

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249495A1 (en) * 2006-03-15 2007-10-25 Xingtao Gao Catalyst composition for reducing gasoline sulfur content in catalytic cracking process
US7960307B2 (en) * 2006-03-15 2011-06-14 Basf Corporation Catalyst composition for reducing gasoline sulfur content in catalytic cracking process
CN100431957C (en) * 2006-09-12 2008-11-12 内蒙古蒙西高岭粉体股份有限公司 Technique of fluidized instant calcinations of kaolin in coal series
WO2011116788A1 (en) 2010-03-25 2011-09-29 Saint Petersburg State University Layered titanates
CN102437322A (en) * 2011-11-23 2012-05-02 陕西科技大学 Method for preparing LiV3O8 microcrystalline through microwave and self-propagation combustion
CN114177880A (en) * 2021-12-23 2022-03-15 安徽建筑大学 Application of sodium vanadate hydrate film as heavy metal adsorption material

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