EP4504384A1 - A process for catalytic filtration of sulfur-containing gases using selective catalytic reduction - Google Patents

A process for catalytic filtration of sulfur-containing gases using selective catalytic reduction

Info

Publication number
EP4504384A1
EP4504384A1 EP23716783.8A EP23716783A EP4504384A1 EP 4504384 A1 EP4504384 A1 EP 4504384A1 EP 23716783 A EP23716783 A EP 23716783A EP 4504384 A1 EP4504384 A1 EP 4504384A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
scr
process according
ozone
bag
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP23716783.8A
Other languages
German (de)
French (fr)
Inventor
Niklas Bengt Jakobsson
Janus Emil MÜNSTER-SWENDSEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of EP4504384A1 publication Critical patent/EP4504384A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8631—Processes characterised by a specific device
    • 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
    • B01D53/90—Injecting reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/104—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20723—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20769—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/915—Catalyst supported on particulate filters
    • 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

Definitions

  • the present invention relates to a novel process for catalytic filtration of sul fur-containing gases using selective catalytic reduction ( SCR) with catalyst regeneration using ozone inj ection .
  • Selective catalytic reduction is primarily a means of converting NOx (nitrogen oxides ) into N2 and H2O .
  • a gaseous reductant typically anhydrous ammonia, aqueous ammonia or urea, is added to a stream of flue gas or exhaust gas and then adsorbed onto a catalyst .
  • urea is used as the reductant
  • CO2 is a reaction product .
  • SCR catalysts are made from various ceramic materials used as a carrier, such as titanium oxide , and active catalytic components are usually either oxides of base metals (such as vanadium, possibly augmented with molybdenum and/or tungsten) , zeolites , or various precious metals (such as palladium and platinum) .
  • base metals such as vanadium, possibly augmented with molybdenum and/or tungsten
  • zeolites such as zeolites
  • precious metals such as palladium and platinum
  • the NOx reduction reaction takes place as the gases pass through the catalyst chamber .
  • the ammonia, or other reductant (such as urea)
  • the chemical equation for a stoichiometric reaction using either anhydrous or aqueous ammonia for a selective catalytic reduction process is as shown below:
  • sulfur is concurrently formed with CO and hydrocarbons as various sulfur oxides (SOx) , typically around 97% S0 2 and up to 3% S0 3 .
  • SOx sulfur oxides
  • S0 3 can react with ammonia to produce ammonium sulfate ( (NH 4 ) 2 SO 4 ) and ammonium bisulfate (NH 4 HSO 4 ) .
  • Certain SCR catalysts such as vanadium-based catalysts, are particularly sensitive to contamination from ammonium sulfate and especially ammonium bisulfate, which is condensed in the pore structure of the catalyst at lower temperatures, thereby physically blocking the pores and deactivating the catalyst.
  • operation of the SCR at a low temperature is desirable because it can provide higher efficiency for power production in the plant.
  • Catalytic bag filters in SCR service are often operating at low temperatures.
  • formation of ammonium bisulfate becomes a major cause for concern, often preventing any use of bag filter SCR.
  • filter bags are stable up to around 230°C which makes periodic heat treatment impossible.
  • WO 2016/028290 describes an exhaust after-treatment system in which a sulfur trioxide trap, configured to selectively capture SO3 from the exhaust gas, is included. This way, the formation of ammonium bisulfate is counteracted.
  • KR 2016 0102691 describes an apparatus and a method for regenerating an SCR system catalyst, which is done by controlled raising of the system temperature up to or above the temperature, at which ammonium bisulfate stuck in the catalyst pores becomes removable.
  • CN 1039 53420 (A) describes a method and a device for the clearing of SCR catalyst sediment particles in the exhaust aftertreatment of a diesel engine
  • CN 1039 20540 (A) describes a method and a device for regenerating an SCR denitration catalyst applied to aftertreatment of diesel engine exhaust .
  • the idea underlying the present invention is to operate a catalytic bag filter in SCR below the dew point of ammonium bisul fate and periodically regenerate the catalyst using ozone inj ection, thereby removing ammonium bisul fate from the catalyst pore structure .
  • the treatment method comprises filling an inactivated flue gas denitration catalyst into a catalyst regeneration reaction bed, introducing a mixed gas of ozone and air into the reaction bed and finishing the catalyst regeneration after oxidation .
  • Ozone trioxygen, O3
  • Ozone trioxygen, O3
  • O3 trioxygen, O3
  • O2 sterili zation and deodoration
  • It is an allotrope of oxygen that is much less stable than the diatomic allotrope O2 , breaking down in the lower atmosphere to normal dioxygen .
  • ozone is a powerful oxidant ( far more so than dioxygen) , it has many industrial applications related to oxidation . However, due to the fact that ozone itsel f is toxic, the residual ozone from these oxida- tion processes must be removed.
  • ozone is a pollutant that cannot be emitted.
  • much research is devoted to find suitable catalysts for oxidation reactions using ozone and also to find effective ways of removing residual ozone following such oxidation reactions.
  • ammonia salts i.e. ammonium chloride (NH4CI) , ammonium nitrate ( (NJh ⁇ NCh) and ammonium bisulfate (NH4HSO4) .
  • NH4CI ammonium chloride
  • NJh ⁇ NCh ammonium nitrate
  • NH4HSO4 ammonium bisulfate
  • SCR installations in coal fired power plants are normally operated at temperatures between 330 and 430°C with typical ammonium bisulfate catalyst dew points between 280 and 320°C.
  • ammonia and sulfuric acid condense as liquid ammonium bisulfate in the catalyst pore structure, which will inhibit the catalyst performance.
  • gaseous sulfuric acid is in equilibrium with SO3, and the ammonium bisulfate dew point therefore depends on water content, ammonia content and SO3 concentration.
  • Ammonium bisulfate has a melting point of 147°C. Formation of ammonia sulfate ( (NJh ⁇ SCy) is thermodynamically more favorable, but analysis of condensed salts has shown that the sulfate is only formed in limited amounts due to kinetic limitations . The inhibition of ammonium bisul fate is reversible , and the ammonium bisul fate is readily evaporated by increasing the catalyst temperature . The bulk dew point at the SCR reactor inlet is typically around 290 ° C, but the observed dew point is higher due to capillary forces in the micropore structure . The ammonium bisul fate dew point decreases through the SCR reactor since ammonia is consumed in the SCR reaction .
  • the catalyst activity is directly related to the extent of pore condensation, which means that the ammonium bisul fate increases gradually as the temperature drops towards the bulk dew point . Operation below the bulk dew point is not an option, except for very low SO3 concentrations in a low dust SCR installation . This is because ammonium bisul fate will condense , not only inside the catalyst pores but also at the catalyst surface , thereby creating a sticky surface which - over time - could lead to plugging of the catalyst .
  • the present invention relates to a process for catalytic filtration of sul fur-containing gases using a selective catalytic reduction (SCR) bag filter consisting of a substrate , a carrier and one or more catalytic materials , wherein
  • SCR selective catalytic reduction
  • the SCR bag filter is operated at a temperature below the dew point of ammonium bisul fate .
  • the catalyst is periodically regenerated using ozone in- j ection, thereby removing ammonium bisul fate from the pore structure of the catalyst .
  • a selective catalytic reduction ( SCR) bag filter to be used in the process of the invention preferably is in the shape of a filter bag assembly comprising multiple fabric filter bags coaxially arranged within an outer filter bag .
  • one or more inner tubular filter bags are separately installed within the outer filter bag and within each other for the removal of dust and particulate matter in the process gas .
  • At least one of the inner tubular filter bags and/or the outer tubular is/are provided with a catalytically active substance .
  • the substrate of the catalyst substance is a fiber structure which can be e . g . woven or knitted glass fibers , and the carrier can be titanium dioxide or another suitable compound .
  • the SCR catalyst will consist of a carrier ( Ti02 ) and a catalytic material comprising vanadium pentoxide (V2O5 ) .
  • the catalytic material can also comprise other compounds , such as W and/or Mo oxides .
  • Bag filters are well suited for the removal of dust and particulate matter from gas streams .
  • Catalytic bag filters have the double utility of being able both to remove particulates from a gas stream and to catalyze one or more desired reactions in the gas .
  • a catalytic bag filter can comprise one single layer of filter fabric, but it will typically comprise two or three layers of filter fabric, each layer containing a tailored catalyst optimi zed for removal of a speci fic kind of compound from the gas that passes through it . Dust and other particulate matter will settle on the surface of the outer bag, from where it can easily be removed.
  • the two or three-layer structure provides the flexibility to tailor different catalytic combinations for different purposes.
  • One of the layers of the catalytic filter bag serves the primary purpose of reducing residual ozone .
  • outer bag refers to the filter bag through which the process gas passes first
  • inner bag refers to the filter bag(s) through which the process gas passes subsequently after having passed through the outer bag .
  • the catalytically active material in at least one of the one and more tubular inner filter bags and/or the outer tubular filter bag is a catalyst composition comprising a vanadium oxide and titania.
  • a vanadium oxide refers to: vanadium ( I I ) oxide (vanadium monoxide) , VO; vanadium ( I I I ) oxide (vanadium sesquioxide or trioxide) , V 2 O 3 ; vanadium ( TV) oxide (vanadium dioxide) , VO2; or vanadium (V) oxide (vanadium pentoxide) , V2O5.
  • the preferred vanadium oxide for use in the process of the invention is vanadium pentoxide (V2O5) .
  • titanium refers to titanium dioxide (Ti02) .
  • the catalytically active material can further comprise palladium or platinum in metallic and/or oxidic form. These catalysts are active both in the removal of VOCs and carbon monoxide and in the removal of nitrogen oxides (NOx) by the SCR reaction with NH 3 .
  • the Pd/V/Ti catalyst is a preferred catalyst because (i) it has a dual functionality (removal of NOx and removal of VOCs) , (ii) it is sulfur-tolerant, and (iii) it has a lower SO2 oxidation activity compared to other catalyst compositions .
  • vanadium oxide is also an active oxidation catalyst.
  • the vanadium oxide catalyst is less selective in the formation of CO2, and some CO is produced during the oxidation reactions. CO cannot be oxidized to CO2 at a feasible reaction rate by contact with the vanadium oxide catalyst, but requires presence of a noble metal catalyst, such as Pd.
  • the outer tubular filter bag and the one or more inner tubular filter bags can be installed in a tube sheet to form a tubular filter bag assembly, wherein a first inner tubular bag, having a smaller diameter than the outer bag, is separately arranged inside the outer bag which forms an ef fective seal between the dirty side and the clean side of the filter .
  • next inner tubular bag with a diameter less than those of the outer bag and the first inner bag, is then separately arranged within the previous inner bag .
  • more than two inner bags may be arranged in the filter bag assembly .
  • any dust and particles present in the process gas will be deposited on the outer surface of the outer tubular filter bag facing the gas .
  • the catalysts loaded onto the outer bag and/or the inner bag ( s ) are ef fectively protected against potential catalyst poisons present in the particles contained in the process gas .
  • the catalyst is periodically regenerated with ozone , whereby ammonium bisul fate is removed from the pore structure of the catalyst .
  • the regeneration is conducted in reverse flow through the catalytic filter bag, i . e . from the center of the bag through the bag and into the bag house or chamber .
  • the ozone to be inj ected can come from various sources , such as an ozone generator .
  • Ozone generators are available in full industrial size, and they are widely used, such as in the pulp and paper industry.
  • the operation temperature of the process of the invention is above the solidification temperature of ammonium bisulfate, i.e. above 147°C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)

Abstract

In a process for catalytic filtration of sulfur-containing gases using a selective catalytic reduction (SCR) bag filter, wherein the SCR bag filter is operated at a temperature below the dew point of ammonium bisulfate, the catalyst is periodically regenerated using ozone injection. In this way, ammonium bisulfate is effectively removed from the pore structure of the catalyst.

Description

Title : A process for catalytic filtration of sulfur-containing gases using selective catalytic reduction
The present invention relates to a novel process for catalytic filtration of sul fur-containing gases using selective catalytic reduction ( SCR) with catalyst regeneration using ozone inj ection .
It is well known that when traditional SCR catalysts are in operation in sul fur-containing flue gases at low temperatures , formation of ammonium bisul fate (NH4HSO4 ) is an important issue regarding design and operation .
Selective catalytic reduction is primarily a means of converting NOx (nitrogen oxides ) into N2 and H2O . A gaseous reductant , typically anhydrous ammonia, aqueous ammonia or urea, is added to a stream of flue gas or exhaust gas and then adsorbed onto a catalyst . When urea is used as the reductant , CO2 is a reaction product .
SCR catalysts are made from various ceramic materials used as a carrier, such as titanium oxide , and active catalytic components are usually either oxides of base metals ( such as vanadium, possibly augmented with molybdenum and/or tungsten) , zeolites , or various precious metals ( such as palladium and platinum) . Another catalyst based on activated carbon, which is applicable for the removal of NOx at low temperatures , has also been developed .
The NOx reduction reaction takes place as the gases pass through the catalyst chamber . Before entering the catalyst chamber the ammonia, or other reductant (such as urea) , is injected and mixed with the gases. The chemical equation for a stoichiometric reaction using either anhydrous or aqueous ammonia for a selective catalytic reduction process is as shown below:
4N0 + 4NH3 + 02 4N2 + 6H2O
2NO2 + 4NH3 + 02 3N2 + 6H2O
NO + NO2 + 2NH3 2N2 + 3H2O with several secondary reactions:
2SO2 + 02 2SO3
2NH3 + S03 + H20 (NH4)2SO4
NH3 + S03 + H20 NH4HSO4
During the combustion process in a power plant, sulfur is concurrently formed with CO and hydrocarbons as various sulfur oxides (SOx) , typically around 97% S02 and up to 3% S03. Thus, fuel with a higher sulfur content tends to produce higher amounts of S03.
As shown above, S03 can react with ammonia to produce ammonium sulfate ( (NH4)2SO4) and ammonium bisulfate (NH4HSO4) . Certain SCR catalysts, such as vanadium-based catalysts, are particularly sensitive to contamination from ammonium sulfate and especially ammonium bisulfate, which is condensed in the pore structure of the catalyst at lower temperatures, thereby physically blocking the pores and deactivating the catalyst. On the other hand, operation of the SCR at a low temperature is desirable because it can provide higher efficiency for power production in the plant.
One proven way to handle this dilemma is to periodically operate the SCR at a higher temperature, where the ammonium bisulfate is released from the catalyst and the catalyst pores are made available for the catalytic reaction. In this way, the catalyst is reactivated.
Catalytic bag filters in SCR service are often operating at low temperatures. For sulfur-containing gases, formation of ammonium bisulfate becomes a major cause for concern, often preventing any use of bag filter SCR. Generally, filter bags are stable up to around 230°C which makes periodic heat treatment impossible.
The issue concerning formation of ammonium bisulfate when SCR catalysts are operated in sulfur-containing flue gases at low temperatures is known from the prior art. Thus, WO 2016/028290 describes an exhaust after-treatment system in which a sulfur trioxide trap, configured to selectively capture SO3 from the exhaust gas, is included. This way, the formation of ammonium bisulfate is counteracted.
KR 2016 0102691 describes an apparatus and a method for regenerating an SCR system catalyst, which is done by controlled raising of the system temperature up to or above the temperature, at which ammonium bisulfate stuck in the catalyst pores becomes removable.
Further, various Chinese documents address the ammonium bisulfate removal issue. Thus, CN 1039 53420 (A) describes a method and a device for the clearing of SCR catalyst sediment particles in the exhaust aftertreatment of a diesel engine , and CN 1039 20540 (A) describes a method and a device for regenerating an SCR denitration catalyst applied to aftertreatment of diesel engine exhaust .
The idea underlying the present invention is to operate a catalytic bag filter in SCR below the dew point of ammonium bisul fate and periodically regenerate the catalyst using ozone inj ection, thereby removing ammonium bisul fate from the catalyst pore structure .
From CN 1021 33547 (A) it is known to use an ozone treatment to regenerate a vanadium-titanium based flue gas denitration catalyst . The treatment method comprises filling an inactivated flue gas denitration catalyst into a catalyst regeneration reaction bed, introducing a mixed gas of ozone and air into the reaction bed and finishing the catalyst regeneration after oxidation .
It is known in the art that ozone is a strong oxidant that can also increase the reactivity of catalysts to convert heavy hydrocarbons at room temperature . Ozone ( trioxygen, O3 ) is known as a strong oxidi zing agent for waste and drinking water treatment , sterili zation and deodoration . It is an allotrope of oxygen that is much less stable than the diatomic allotrope O2 , breaking down in the lower atmosphere to normal dioxygen . Since ozone is a powerful oxidant ( far more so than dioxygen) , it has many industrial applications related to oxidation . However, due to the fact that ozone itsel f is toxic, the residual ozone from these oxida- tion processes must be removed. Moreover, being quite harmful to animal and plant tissue even in concentrations as low as around 100 ppb, ozone is a pollutant that cannot be emitted. For these reasons, much research is devoted to find suitable catalysts for oxidation reactions using ozone and also to find effective ways of removing residual ozone following such oxidation reactions.
In the presence of ammonia, the acid gases in the sulfur- containing flue gas form ammonia salts, i.e. ammonium chloride (NH4CI) , ammonium nitrate ( (NJh^NCh) and ammonium bisulfate (NH4HSO4) . In most cases, NH4HSO4 has the highest dew point, but in waste incineration units with HC1 concentrations of several hundred ppm NH4CI, condensation determines the minimum temperature. SCR installations in coal fired power plants are normally operated at temperatures between 330 and 430°C with typical ammonium bisulfate catalyst dew points between 280 and 320°C. Below the dew point, ammonia and sulfuric acid condense as liquid ammonium bisulfate in the catalyst pore structure, which will inhibit the catalyst performance. At sufficiently high temperatures, gaseous sulfuric acid is in equilibrium with SO3, and the ammonium bisulfate dew point therefore depends on water content, ammonia content and SO3 concentration.
Ammonium bisulfate has a melting point of 147°C. Formation of ammonia sulfate ( (NJh^SCy) is thermodynamically more favorable, but analysis of condensed salts has shown that the sulfate is only formed in limited amounts due to kinetic limitations . The inhibition of ammonium bisul fate is reversible , and the ammonium bisul fate is readily evaporated by increasing the catalyst temperature . The bulk dew point at the SCR reactor inlet is typically around 290 ° C, but the observed dew point is higher due to capillary forces in the micropore structure . The ammonium bisul fate dew point decreases through the SCR reactor since ammonia is consumed in the SCR reaction .
The catalyst activity is directly related to the extent of pore condensation, which means that the ammonium bisul fate increases gradually as the temperature drops towards the bulk dew point . Operation below the bulk dew point is not an option, except for very low SO3 concentrations in a low dust SCR installation . This is because ammonium bisul fate will condense , not only inside the catalyst pores but also at the catalyst surface , thereby creating a sticky surface which - over time - could lead to plugging of the catalyst .
So the present invention relates to a process for catalytic filtration of sul fur-containing gases using a selective catalytic reduction ( SCR) bag filter consisting of a substrate , a carrier and one or more catalytic materials , wherein
- the SCR bag filter is operated at a temperature below the dew point of ammonium bisul fate , and
- the catalyst is periodically regenerated using ozone in- j ection, thereby removing ammonium bisul fate from the pore structure of the catalyst .
A selective catalytic reduction ( SCR) bag filter to be used in the process of the invention preferably is in the shape of a filter bag assembly comprising multiple fabric filter bags coaxially arranged within an outer filter bag . Inside the outer filter bag, one or more inner tubular filter bags are separately installed within the outer filter bag and within each other for the removal of dust and particulate matter in the process gas . At least one of the inner tubular filter bags and/or the outer tubular is/are provided with a catalytically active substance . The substrate of the catalyst substance is a fiber structure which can be e . g . woven or knitted glass fibers , and the carrier can be titanium dioxide or another suitable compound . Typically, the SCR catalyst will consist of a carrier ( Ti02 ) and a catalytic material comprising vanadium pentoxide (V2O5 ) . The catalytic material can also comprise other compounds , such as W and/or Mo oxides .
Bag filters are well suited for the removal of dust and particulate matter from gas streams . Catalytic bag filters have the double utility of being able both to remove particulates from a gas stream and to catalyze one or more desired reactions in the gas . A catalytic bag filter can comprise one single layer of filter fabric, but it will typically comprise two or three layers of filter fabric, each layer containing a tailored catalyst optimi zed for removal of a speci fic kind of compound from the gas that passes through it . Dust and other particulate matter will settle on the surface of the outer bag, from where it can easily be removed. The two or three-layer structure provides the flexibility to tailor different catalytic combinations for different purposes. One of the layers of the catalytic filter bag serves the primary purpose of reducing residual ozone .
The term "outer bag" refers to the filter bag through which the process gas passes first, and the term "inner bag" refers to the filter bag(s) through which the process gas passes subsequently after having passed through the outer bag .
The catalytically active material in at least one of the one and more tubular inner filter bags and/or the outer tubular filter bag is a catalyst composition comprising a vanadium oxide and titania.
The term "a vanadium oxide" refers to: vanadium ( I I ) oxide (vanadium monoxide) , VO; vanadium ( I I I ) oxide (vanadium sesquioxide or trioxide) , V2O3; vanadium ( TV) oxide (vanadium dioxide) , VO2; or vanadium (V) oxide (vanadium pentoxide) , V2O5.
The preferred vanadium oxide for use in the process of the invention is vanadium pentoxide (V2O5) .
The term "titania" refers to titanium dioxide (Ti02) .
The catalytically active material can further comprise palladium or platinum in metallic and/or oxidic form. These catalysts are active both in the removal of VOCs and carbon monoxide and in the removal of nitrogen oxides (NOx) by the SCR reaction with NH3.
The Pd/V/Ti catalyst is a preferred catalyst because (i) it has a dual functionality (removal of NOx and removal of VOCs) , (ii) it is sulfur-tolerant, and (iii) it has a lower SO2 oxidation activity compared to other catalyst compositions .
It is known that the oxidation activity of a Pd-containing catalyst is reduced in the presence of a few ppm of NH3. It is also known that, besides being an active catalyst in the NH3-SCR of NOx, vanadium oxide is also an active oxidation catalyst. Compared to the precious metal catalysts, like the Pd catalyst, the vanadium oxide catalyst is less selective in the formation of CO2, and some CO is produced during the oxidation reactions. CO cannot be oxidized to CO2 at a feasible reaction rate by contact with the vanadium oxide catalyst, but requires presence of a noble metal catalyst, such as Pd. Thus, if NH3 is present in the gas, then it is preferred to catalyze the outer filter bag with a V/Ti catalyst and at least one of the inner filter bags with a Pd/V/Ti catalyst if CO is present in the process gas or formed by the catalytical oxidation of VOCs in the outer filter bag. Thus, by loading an inner filter bag with a Pd/V/Ti catalyst, CO and any remaining VOCs will effectively be oxidized to CO2. In this way, the load of expensive noble metals in the inner filter bags can be limited to a minimum. The outer tubular filter bag and the one or more inner tubular filter bags can be installed in a tube sheet to form a tubular filter bag assembly, wherein a first inner tubular bag, having a smaller diameter than the outer bag, is separately arranged inside the outer bag which forms an ef fective seal between the dirty side and the clean side of the filter .
The next inner tubular bag, with a diameter less than those of the outer bag and the first inner bag, is then separately arranged within the previous inner bag . Optionally more than two inner bags may be arranged in the filter bag assembly .
Any dust and particles present in the process gas will be deposited on the outer surface of the outer tubular filter bag facing the gas . Thus , the catalysts loaded onto the outer bag and/or the inner bag ( s ) are ef fectively protected against potential catalyst poisons present in the particles contained in the process gas .
In the process of the invention, the catalyst is periodically regenerated with ozone , whereby ammonium bisul fate is removed from the pore structure of the catalyst .
When the catalyst is regenerated with ozone , the regeneration is conducted in reverse flow through the catalytic filter bag, i . e . from the center of the bag through the bag and into the bag house or chamber .
The ozone to be inj ected can come from various sources , such as an ozone generator . Ozone generators are available in full industrial size, and they are widely used, such as in the pulp and paper industry.
The operation temperature of the process of the invention is above the solidification temperature of ammonium bisulfate, i.e. above 147°C.

Claims

Claims :
1 . A process for catalytic filtration of sul fur-containing gases using a selective catalytic reduction ( SCR) bag filter consisting of a substrate , a carrier and one or more catalytic materials , wherein
- the SCR bag filter is operated at a temperature below the dew point of ammonium bisul fate , and
- the catalyst is periodically regenerated using ozone in- j ection, thereby removing ammonium bisul fate from the pore structure of the catalyst .
2 . Process according to claim 1 , wherein the SCR bag filter is an assembly consisting of an outer tubular filter bag and one or more inner tubular filter bags installed in a tube sheet .
3 . Process according to claim 1 or 2 , wherein the catalyst consists of a carrier and one or more catalytic materials .
4 . Process according to any of the claims 1-3 , wherein the carrier is Ti02 , and the catalytic materials are selected from the vanadium oxides VO, V2O3, VO2 and V2O5.
5. Process according to claim 3 or 4, wherein the cat- alyst further comprises Pd in metallic or oxidic form.
6. Process according to claim 1, wherein one layer of the SCR bag filter serves the primary purpose of reducing any residual ozone.
7. Process according to claim 1, wherein the operation temperature is above the solidification temperature of ammonium bisulfate.
8. Process according to claim 1, wherein the catalyst is periodically regenerated with ozone, thereby removing ammonium bisulfate from the pore structure of the catalyst.
9. Process according to claim 8, wherein the ozone regeneration is conducted by flowing ozone through the SCR bag filter from the clean side thereof.
EP23716783.8A 2022-04-01 2023-03-29 A process for catalytic filtration of sulfur-containing gases using selective catalytic reduction Withdrawn EP4504384A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA202200306 2022-04-01
PCT/EP2023/058109 WO2023186965A1 (en) 2022-04-01 2023-03-29 A process for catalytic filtration of sulfur-containing gases using selective catalytic reduction

Publications (1)

Publication Number Publication Date
EP4504384A1 true EP4504384A1 (en) 2025-02-12

Family

ID=86006609

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23716783.8A Withdrawn EP4504384A1 (en) 2022-04-01 2023-03-29 A process for catalytic filtration of sulfur-containing gases using selective catalytic reduction

Country Status (5)

Country Link
EP (1) EP4504384A1 (en)
JP (1) JP2025511226A (en)
CN (1) CN118946396A (en)
TW (1) TW202342155A (en)
WO (1) WO2023186965A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118203950B (en) * 2024-02-28 2025-09-16 远富新(厦门)节能新材料科技有限公司 Flue gas dedusting and denitration system for medium-low temperature sulfur-containing and water-containing environment and filter bag manufacturing method

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006103040A1 (en) * 2005-04-01 2006-10-05 Haldor Topsøe A/S Process for catalytic reduction of nox by ammonia in presence of so3 in the gas
CN102133547B (en) 2011-03-02 2013-03-20 华南理工大学 Ozone treatment regeneration method and device for vanadium titanium-based flue gas denitration catalyst
AR100119A1 (en) * 2014-03-21 2016-09-14 Haldor Topsoe As MOUNTING FILTER BAGS
CN103920540B (en) 2014-04-17 2015-11-25 宁波大学 The renovation process of SCR denitration and device in a kind of diesel exhaust aftertreatment
CN103953420B (en) 2014-04-17 2016-05-25 宁波大学 Sweep-out method and the device of SCR catalyst deposit particulate in diesel exhaust aftertreatment
WO2016028290A1 (en) 2014-08-20 2016-02-25 Cummins Emission Solutions, Inc. Sulfur trioxide trap for use in preventing catalyst deactivation by ammonium sulfate/bisulfate
KR20160102691A (en) 2015-02-23 2016-08-31 현대중공업 주식회사 Apparatus and method for regenerating catalyst of scr system
TW201838708A (en) * 2017-03-02 2018-11-01 丹麥商托普索公司 Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant
US10940471B1 (en) * 2019-10-30 2021-03-09 W. L. Gore & Associates, Inc. Catalytic efficiency of flue gas filtration

Also Published As

Publication number Publication date
CN118946396A (en) 2024-11-12
WO2023186965A1 (en) 2023-10-05
TW202342155A (en) 2023-11-01
JP2025511226A (en) 2025-04-15

Similar Documents

Publication Publication Date Title
Ye et al. Recent trends in vanadium-based SCR catalysts for NOx reduction in industrial applications: stationary sources
JP3935547B2 (en) Exhaust gas treatment method and exhaust gas treatment apparatus
EP1115471B1 (en) Process and catalyst/sorber for treating sulfur compound containing effluent
CN101300068B (en) Vanadium/titania catalyst comprising natural manganese ore for removal of nitrogen oxides and dioxins over a wide operating temperature range and method of using the catalyst
US10286360B2 (en) Method for cleaning process off- or engine exhaust gas
EP2044997B1 (en) Apparatus for removing of trace of toxic substance from exhaust gas and method of operating the same
JP5051977B2 (en) Device for removing trace harmful substances in exhaust gas and operation method thereof
JP2018126674A (en) Exhaust gas treatment system and exhaust gas treatment method
US20210101111A1 (en) Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant
CA2976143C (en) Catalyzed ceramic candle filter and method of cleaning process off- or exhaust gases
EP4504384A1 (en) A process for catalytic filtration of sulfur-containing gases using selective catalytic reduction
WO2010016392A1 (en) Apparatus for treating discharge gas and system for treating discharge gas
CN120733559B (en) Ceramic fiber pipe and preparation method thereof
JP2019525826A (en) Filter bag assembly containing catalyst material
TW201838707A (en) Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant
CN103623682A (en) HC-LSCR/O-AS engineering system for fume cleaning
DK202200308A1 (en) A process for selective catalytic reduction (SCR) of sulfur-containing gases
JP2008030017A (en) Removal apparatus of trace harmful substance in exhaust gas and its operation method
CA3180975A1 (en) Catalytic oxidation of carbon black exhaust gas
Blumrich et al. The DESONOX/REDOX-process for flue gas cleaning: A flue gas purification process for the simultaneous removal of NOx and SO2 resp. CO and UHC
US20130004396A1 (en) Processes and apparatuses for eliminating elemental mercury from flue gas using deacon reaction catalysts at low temperatures
TWI637783B (en) Catalyzed ceramic candle filter and method for cleaning of off- or exhaust gases
Weber et al. High and Low Dust SCR Processes
JPS588890B2 (en) Chitsusosan Kabutsurenzokushiyorihohou

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240925

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20250513