WO2015176101A1 - Procédé intégré de réduction des oxydes de souffre et des oxydes d'azote - Google Patents

Procédé intégré de réduction des oxydes de souffre et des oxydes d'azote Download PDF

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WO2015176101A1
WO2015176101A1 PCT/AU2015/000247 AU2015000247W WO2015176101A1 WO 2015176101 A1 WO2015176101 A1 WO 2015176101A1 AU 2015000247 W AU2015000247 W AU 2015000247W WO 2015176101 A1 WO2015176101 A1 WO 2015176101A1
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flue gas
sox
sorbent
nox
catalyst
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PCT/AU2015/000247
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English (en)
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Jianglong YU
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Newcastle Innovation Limited
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Priority claimed from AU2014901906A external-priority patent/AU2014901906A0/en
Application filed by Newcastle Innovation Limited filed Critical Newcastle Innovation Limited
Priority to AU2015263824A priority Critical patent/AU2015263824A1/en
Priority to CN201580026561.1A priority patent/CN106413883A/zh
Publication of WO2015176101A1 publication Critical patent/WO2015176101A1/fr

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    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B01D53/565—Nitrogen oxides by treating the gases with solids
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • 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
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1122—Metals
    • 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
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • 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
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating

Definitions

  • the present invention relates to a method, apparatus and system for reducing the concentration of sulfur oxides ("SOx”) and nitrogen oxides ("NOx”) in the flue gases emitted by the combustion of fossil fuels in, for instance, coal- fired power plants. As such, the present invention stands to bring forth perceptible
  • coal- fired power plants cause great harm to the environment.
  • Such power stations use rotating machinery to convert the heat energy of combustion into mechanical energy, which in turn operates an electrical generator.
  • the prime mover may be a steam turbine, a gas turbine or, in small plants, a reciprocating internal combustion engine. All plants use the energy extracted from expanding gas (i.e., steam or combustion gases).
  • oxides of carbon i.e., C0 2 , CO
  • C0 2 carbon dioxide
  • CO carbon dioxide
  • acid rain is caused by the emission of NOx and SOx. These gases may be only mildly acidic themselves, yet when they react with the atmosphere, they create acidic compounds such as sulfurous acid, nitric acid and sulfuric acid which then fall as rain. Stricter regulatory emission laws and a decline in heavy industries have to some extent reduced the environmental hazards associated with this problem - nonetheless, acid rain remains a significant environmental concern.
  • ESA European Environment Agency
  • NOx and SOx are two of the chief pollutants discharged into the atmosphere in flue gases.
  • Flue gas stacks serve to disperse exhaust pollutants and thereby reduce the concentration of such pollutants to levels required by governmental environmental regulations.
  • concentration is the solution to pollution
  • flue gas stacks are not, of themselves, the answer - the same net amount of SOx and NOx eventually ends up in the atmosphere.
  • FGD flue gas desulfurisation
  • SOx remediation technologies have evolved to encompass a variety of methods, including: "wet scrubbing” ⁇ i.e., using a slurry of alkaline sorbent, usually limestone or lime, or seawater to “scrub” gases); “spray-dry scrubbing” ⁇ i.e., using similar sorbent slurries); wet sulfuric acid (“WSA”) processes, which recover sulfur in the form of commercial quality sulfuric acid; “SNOX” FGD (discussed below); and dry sorbent injection systems. For a typical coal- fired power station, FGD processes may remove up to 95% of the SOx in the flue gases.
  • SNOX FGD removes sulfur dioxide, nitrogen oxides and particulates from flue gases.
  • the sulfur is recovered as concentrated sulfuric acid and the nitrogen oxides are reduced to free nitrogen.
  • the process is based on the well-known WSA process for recovering sulfur from various process gases in the form of commercial quality sulfuric acid.
  • SOx and NOx are removed separately, in different reactors.
  • the process is based on catalytic reactions and does not produce any waste, except for the separated dust. In addition, the process can handle other sulfurous waste streams.
  • the SNOX process catalytically reduces both SOx and
  • the SNOX technology is especially suitable for cleaning flue gases from the combustion of high-sulfur fuels.
  • SNOX is a very energy- efficient means to convert the NOx in the flue gas into nitrogen and the SOx into concentrated sulfuric acid of commercial quality without using any absorbents and without producing significant waste.
  • FGD systems employ two stages: one for fly ash removal ⁇ i.e., filtering of the particulate matter) and the other for SOx removal.
  • fly ash removal device either an electrostatic precipitator or a wet scrubber, and then into the SOx absorber.
  • the SOx is first reacted with the sorbent, and then the flue gas passes through a particulate control device.
  • Another design consideration associated with wet FGD systems is that the flue gas exiting the absorber is saturated with water and still contains some SOx. These gases are highly corrosive to any downstream equipment such as fans, ducts, and stacks.
  • SOx (specifically, S0 2 ) is an acidic gas; the sorbent slurries or other materials used to remove the S0 2 from the flue gases are thereby typically alkaline.
  • the problem is that the slurries are circulated through the scrubber instead of a solution; this makes it harder on the equipment.
  • wet scrubbing with a magnesium hydroxide slurry produces magnesium sulfite (equation 3); and wet scrubbing with sodium hydroxide (equation 4) is limited to smaller combustion units because it is more expensive than lime, but it has the advantage that it forms a solution rather than a slurry; this makes it easier to operate. It produces a "spent caustic" solution of sodium sulfite/bisulfite (depending upon the pH), or sodium sulfate that must be disposed of.
  • the calcium sulfite can be further oxidised to produce saleable gypsum (equation 5):
  • venturi scrubbers For simultaneous removal of S0 2 and fly ash, venturi scrubbers can be used. Although removal of both particulate matter and S0 2 in one vessel can be economical, the problems of high pressure drops and finding a scrubbing medium to remove heavy loadings of fly ash are clear drawbacks. However, in cases where the particle concentration is low, such as from oil-fired units, it can be more effective to remove particulate matter and S0 2 simultaneously. Of course, this does not extend to the products of coal combustion.
  • a packed bed scrubber consists of a tower with packing material inside to maximise the contact area between the dirty gas and liquid.
  • Packed towers typically operate at much lower pressure drops than venturi scrubbers and are therefore somewhat cheaper to operate. They also typically offer higher S0 2 removal efficiency. The drawback is that they have a greater tendency to plug up if particulate matter is present in excess in the exhaust air stream, which makes them unsuitable for remediating flue gases from coal- fired power stations.
  • a flue gas remediation process may effectively remove SOx and NOx from a flue gas within a single reactor, thereby aiding efficiencies.
  • such a process would be a dry, or substantially dry method, avoiding the need for vast quantities of water and the subsequent and damaging contamination thereof.
  • the present invention is directed to a means of "removing" SOx and NOx from flue gases.
  • "removing” is not to be construed as an absolute term, i.e., the invention does not need to reduce the concentration of SOx and/or NOx from its initial concentration to 0% in order to adequately "work".
  • remediation, per se is properly considered with respect to SOx and NOx
  • the invention properly relates to a method of reducing the concentration of SOx and/or NOx in flue gases - preferably to levels in accordance with environmental regulations.
  • the SOx concentration in flue gases produced in a coal-fired power plant is typically about 1200-2400 ppmv; the concentration of NOx is typically about 100-500 ppmv.
  • FIG. 1 is a schematic representation of a preferred embodiment of the present invention.
  • the overall process flow can be summarised as depicted (AH: air heater; ESP: electrical static precipitator; FB: fixed bed).
  • FIG. 2 is a schematic diagram depicting the process of the present invention. Flue gas and the sorbent catalyst are actively brought into chemical contact at a temperature of between 300 °C and 400 °C in a counter-flow relationship within the reactor Rl;
  • Figure 3 is a graph depicting de-SOx efficiency of the copper-based
  • Figure 4 is a graph depicting de-NOx efficiency of the copper-based (Cu x iFe x2 Mn X3 Ce x4 Zn x5 ) sorbent catalyst over time. Two temperatures were tested (Tl 350 °C; T2 300 °C). The catalyst worked at optimum efficiency for nearly 900 hours (for T2) and about 1400 hours (for Tl); it would then be subjected to regeneration, as described below.
  • a catalyst sorbent of the general formula Co x iFe X2 Mn x3 Ce X4 Zn x5 wherein: xl is 30-60%; x2 is 20-40%; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • the catalyst is operatively supported on an activated char.
  • the activated char has a mesoporosity of about 40-60%.
  • the mesoporous nature of the char provides, on the on hand, a substrate upon which the catalyst sorbent is deposited - and on the other hand, provides the additional advantage that trace mercury present in the flue gas adsorbs onto said active char support, thereby to actively remove mercury from the flue gas.
  • the catalyst is adapted for use in a process for lessening the concentration of sulfur oxides (“SOx”) and nitrogen oxides (“NOx”) in flue gas.
  • SOx sulfur oxides
  • NOx nitrogen oxides
  • the process takes place at a temperature of between about 300 °C and about 400 °C.
  • the mesoporosity provides for mercury to adsorb onto said active char support, thereby to actively remove mercury from a flue gas.
  • the catalyst sorbent is adapted for recycling or regeneration, thereby to return a spent catalyst sorbent to its original state, having its original catalytic activity.
  • a reactor comprising a sorbent bed
  • said sorbent bed comprises an active char support of the general formula Cu x iFe x2 Mn X3 Ce X4 Zn X 5, wherein: xl is 30-60%; x2 is 20- 40%; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • the sorbent bed comprises an active char support of the general formula Co x iFe X2 Mn x3 Ce X4 Zn x5 , wherein: xl is 30-60%>; x2 is 20-40%>; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • the method further comprises the step of exhausting said remediated flue gas to a flue gas stack.
  • the method further comprises the step of extracting, from a regeneration unit operatively associated with said sorbent bed, sulfuric acid as a by-product of the reduction of said SOx and said NOx.
  • said active char support has a mesoporosity of about 40- 60%).
  • said mesoporosity provides for mercury present within said feed stream of flue gas to adsorb onto said active char support, thereby to actively remove mercury from said flue gas.
  • the parameters of the process are as follows: residence time 2-16 minutes; operating temperature 350-400 °C for the de-SOx/de-NOx unit; and 750-850 °C for the regeneration unit.
  • the process can be characterised as being substantially
  • the process takes place at a temperature of between about 300 °C and about 400 °C.
  • the flue gas and the catalyst sorbent are chemically associated in a counter-flow arrangement.
  • spent catalyst sorbent in said regeneration unit, is heated to flash sulfur trioxide gas, said sulfur trioxide then reacted with water to form said sulfuric acid; and the resultant regenerated catalyst sorbent returned to said reactor.
  • the flashing of sulfur trioxide occurs at a temperature of about 750 °C.
  • spent catalyst is able to be regenerated up to about 1000 times.
  • a catalyst sorbent operatively supported on an active char support, the catalyst of the general formula Cu x iFe x2 Mn X3 Ce X4 Zn X 5, wherein: xl is 30-60%; x2 is 20-40%>; x3 is 10-15%>; x4 is 1-5%; and x5 is 0.1-0.3%), in a process for lessening the concentration of sulfur oxides ("SOx”) and nitrogen oxides (“NOx”) in flue gas.
  • SOx sulfur oxides
  • NOx nitrogen oxides
  • the active char support is of the general formula Co x iFe X2 Mn x3 Ce X4 Zn x5 , wherein: xl is 30-60%; x2 is 20-40%; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • said active char support has a mesoporosity of about 60%.
  • said mesoporosity provides for mercury within said flue gas to adsorb onto said active char support, thereby to actively remove mercury from said flue gas.
  • the flue gas and the catalyst sorbent are chemically associated in a counter-flow arrangement.
  • use within the process can be characterised as substantially "dry” by comparison with a SNOX FGD process.
  • an apparatus for lessening the concentration of sulfur oxides (“SOx”) and nitrogen oxides (“NOx”) in flue gas comprising:
  • said sorbent bed comprises an active char support of the general formula Cu x iFe X2 Mn x3 Ce X4 Zn x5 , wherein: xl is 30-60%>; x2 is 20- 40%; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • the active char support is of the general formula
  • the apparatus further comprises means for exhausting said remediated flue gas to a flue gas stack.
  • the apparatus further comprises a regeneration unit operatively associated with said sorbent bed; and means for extracting sulfuric acid therefrom, said acid being a by-product of the reduction of said SOx and said NOx.
  • the active char support has a mesoporosity of about 60%.
  • the mesoporosity provides for mercury present within said feed stream of flue gas to adsorb onto said active char support, thereby to actively remove mercury from said flue gas.
  • the apparatus is for use within a substantially “dry” process for lessening the concentration of sulfur oxides (“SOx”) and nitrogen oxides (“NOx”) in flue gas by comparison with a SNOX FGD process.
  • SOx sulfur oxides
  • NOx nitrogen oxides
  • the apparatus is adapted for operation at a temperature of between about 300 °C and about 400 °C.
  • said flue gas and said catalyst sorbent are chemically associated in a counter-flow arrangement.
  • the invention also relates to a process for making the catalyst sorbents described above.
  • a method for making the catalyst sorbents described above comprises the general steps of: loading the active components into lignite coal; then gasifying the coal using steam at about 850 °C for about 20-30 minutes. It is found that the catalyst sorbents produced by such process are chemically reactive and facilitate high de-SOx and de-NOx removal efficiencies.
  • a catalyst sorbent as defined according to the first aspect of the present invention, said method comprising the steps of:
  • DIFGDSN dry integrated flue gas de-SOx and de-NOx technology
  • the overall efficiency of the simultaneous SOx and NOx removal will meet with governmental environmental standards.
  • the technology is applicable to both the retrofit of existing power plants (e.g., to replace the old FGD units) and new power plants in which both de-SOx and de-NOx are now mandatory under government environmental requirements.
  • the inventive process has at least the following distinguishing characteristics over conventional de-SOx/de-NOx processes: Firstly, the FB reactor unit uses an inventive sorbent supported on an activated char. Accordingly, the new composition of active components is defined according to the general formula:
  • the new composition of active components is defined according to the general formula: Co x iFex2Mn X3 Ce X4 Zn X 5, wherein: xl is 30- 60%; x2 is 20-40%; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • the new composition of active components is defined according to the general formula: Co x iFex2Mn X3 Ce X4 Zn X 5, wherein: xl is 30- 60%; x2 is 20-40%; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • the five components are impregnated onto the activated char support.
  • the active char support has a mesoporosity of about 60%, which permits high reactivity of the active constituents and conveniently facilitates the adsorption of mercury thereupon.
  • the FB reactor using the inventive sorbent can simultaneously remove SOx and NOx (and mercury) from a flue gas, which cannot be achieved using existing flue gas cleansing technologies and processes.
  • the NOx is reduced to nitrogen gas through the catalytic reactions between NOx and the carbon in the activated char.
  • the activated char support having mesoporosity, also permits the adsorption of the mercury with subsequent removal thereof from the flue gas.
  • the above-described invention is clearly industrially-applicable. Existing power stations could be retrofitted with this technology and/or the inventive process could be incorporated within designs for new power stations.
  • the invention is especially applicable to power stations in regions of the world where a low-grade (highly contaminated) coal is used; this in turn results in more contaminated flue gas, having relatively high concentrations of SOx and NOx.
  • the inventive process is represented according to a schematic diagram.
  • the process utilises two reactors. Firstly, there is provided a fixed-bed reactor (Rl) in which de-SOx and de- NOx of flue gases are effected; and a second fixed-bed reactor (R2), which is the regeneration unit described in further detail below.
  • Rl fixed-bed reactor
  • R2 second fixed-bed reactor
  • the process can be effected both on a continuous or a batch basis, it has been described hereinafter as a continuous process.
  • Reactor Rl is a fixed bed reactor comprising a catalyst sorbent (1) of the general formula Cu x iFex2Mn X3 Ce X4 Zn X 5, wherein: xl is 30-60%; x2 is 20-40%; x3 is 10-15%; x4 is 1-5%; and x5 is 0.1-0.3%.
  • the sorbent catalyst is operatively supported on an activated char having a mesoporosity of about 40-60%.
  • cobalt can be used instead of copper.
  • the copper sorbent catalyst is used.
  • Flue gas (2) generated by the burning of coal enters the reactor (Rl) via a flue gas inlet port (3).
  • the temperature of the gas (2) is typically about 130 °C prior to entering the reactor.
  • the temperature within the reactor (Rl) is generally about 300- 400 °C; as such, the flue gas gains significant kinetic energy from the heat ramp upon entry into the reactor (Rl).
  • the reactor (Rl) is equipped with a sorbent exit port (4), through which spent sorbent catalyst (1) is transmitted, preferably under gravity, to the regeneration reactor (R2) via a conduit (5).
  • the temperature within the regeneration reactor (R2) is about 750 °C; such high temperature vaporises S0 3 adsorbed previously onto the surface of the sorbent catalyst (1).
  • the vaporised SO 3 then exits the regeneration reactor (R2) via a conduit (6) to a further reactor (R3) whereupon it is dissolved into water to form sulfuric acid, which in turn exits the reactor (R3) via a conduit (7).
  • the concentrated sulfuric acid is preferably commercial grade - and can be on-sold if desired.
  • the regeneration reactor has an exit port (8) through which regenerated sorbent catalyst (1) exits the reactor (R2).
  • the regenerated catalyst is then transmitted back to the reactor (Rl) via a conduit (9); this could be under pressure or by mechanical transmission.
  • the regenerated sorbent catalyst (1) then enters the reactor (Rl) at an entry point (10) near the top of the reactor. From there, it moves downward under gravity.
  • the sorbent catalyst (1) performs (with respect to the schematic depicted in Figure 2) a "clockwise" cyclic movement from the reactor (Rl) to the reactor (R2), back to the reactor (Rl) - and so forth.
  • the "raw” gas i.e., containing a relatively high concentration of NOx and SOx
  • the flue gas (2) moves "upwards” as depicted by the dotted path (11).
  • the relatively raw (i.e., SOx and NOx concentrations are relatively high) flue gas (2) entering the reactor (Rl) first encounters relatively spent sorbent catalyst (1) (i.e., near the bottom of the reactor (Rl)); this spent sorbent catalyst (1) is essentially at the end of its cycle - and soon moves to the regeneration reactor (R2) as described above.
  • the relatively raw flue gas moves upward through the reactor (Rl) in counter- flow to the sorbent (1), thereby encountering progressively fresher (less spent) catalyst (1) as it progresses upward.
  • the remediated flue gas (1) then exits the reactor (Rl) via an exit port (12).
  • the temperature of the remediated gas is around 300 °C - and the remediated gas can then be exhausted to a flue gas stack (not shown) - or can undergo secondary cleansing (e.g., to remove particulate matter) via an ESP, etc.
  • the sorbent catalyst (1) can be regenerated via reactor (R2) at least around 1000 times before it loses its effectiveness.
  • R2 reactor
  • the mesoporosity typically 40-60% traps mercury within the pores. Mercury is present in flue gases only in trace amounts. However, as will be appreciated, after 1000 or so passes, the pores do become somewhat clogged.
  • the optimum residence time for the flue gas within the reactor (Rl) i.e., the time taken to effect de-SOx and de-NOx is somewhere between 2 and 16 minutes.
  • the industrial applicability of the present invention is palpable.
  • the scale of environmental damage caused by the combustion of fossil fuels has been identified above - and any invention that provides means by which such damage may be lessened or even reversed has clear industrial potential.

Abstract

La présente invention concerne un procédé et un appareil permettant de réduire la concentration en oxydes de soufre (« SOx ») et en oxydes d'azote (« NOx ») dans des gaz de carneau. Le procédé comprend d'une manière générale l'association chimique d'un flux de gaz de carneau à un lit sorbant, afin de réduire ainsi chimiquement et de façon active les SOx et les NOx et de fournir un flux d'échappement de gaz de carneau pratiquement décontaminé (« dé-SOx » et « dé-NOx ») ; le lit sorbant comprenant un support de charbon actif de formule générale Cux1Fex2MnX3CeX4ZnX5 ou CoX1Fex2MnX3CeX4ZnX5, dans laquelle : x1 représente de 30 à 60 % ; x2 représente de 20 à 40 % ; x3 représente de 10 à 15 % ; x4 représente de 1 à 5 % ; et x5 représente de 0,1 à 0,3 %.
PCT/AU2015/000247 2014-05-22 2015-04-28 Procédé intégré de réduction des oxydes de souffre et des oxydes d'azote WO2015176101A1 (fr)

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CN201580026561.1A CN106413883A (zh) 2014-05-22 2015-04-28 集成脱硫氧化物与脱氮氧化物工艺

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CN111569834A (zh) * 2020-06-01 2020-08-25 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) 一种粗氯乙烯气体除汞吸附剂

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US11577199B2 (en) * 2020-05-18 2023-02-14 China Huaneng Group Co., Ltd Method for desulphurizating and denitrating flue gas in integrated manner based on low-temperature adsorption

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