WO2014029578A1 - Method and catalyzed filter element with improved alkali-resistance for flue gas cleaning - Google Patents
Method and catalyzed filter element with improved alkali-resistance for flue gas cleaning Download PDFInfo
- Publication number
- WO2014029578A1 WO2014029578A1 PCT/EP2013/065577 EP2013065577W WO2014029578A1 WO 2014029578 A1 WO2014029578 A1 WO 2014029578A1 EP 2013065577 W EP2013065577 W EP 2013065577W WO 2014029578 A1 WO2014029578 A1 WO 2014029578A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- filter element
- flue gas
- calcium
- alkali metal
- alkaline powder
- Prior art date
Links
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/707—Additives or dopants
-
- 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 is directed in general to the clean- ing of flue gases containing alkali metals or alkali metal compounds and to catalysed filter elements resistant against poisoning by alkali metals or alkali metal com ⁇ pounds.
- the invention provides a method and a catalysed filter element with improved alkali metal re- sistance filter elements for the removal of particulate matter and environmental or health harmful compounds from flue or off-gases containing alkali metals or alkali metal compounds .
- Deactivation of catalysts is fast, in particular SCR cata ⁇ lysts used in the treatment of flue gases from e.g.
- the deactivation is due to the alkali metals fraction of the fly ash contained in the flue gas that acts as a cata ⁇ lyst poison.
- the interaction between the alkali metals or alkali metal compounds and the active sites of the catalyst is facilitated by the fact that these alka- li metals are present in water soluble compounds and there ⁇ fore prone to "jump" from the ash particle onto the cata ⁇ lyst surface via acid-base reaction between the particle and the catalyst.
- the alkali metals or alkali metal compounds further penetrate into the catalyst wall by surface diffusion, strongly bound to the catalyst active sites and deactivate the catalyst.
- the reaction be ⁇ tween the ash particle and the catalyst is due to the di- rect physical contact between those two species facilitated by increasing temperatures.
- the deactivation rate of the catalyst is very fast at temperatures above 200°C. In fact, both the acid-base reaction taking place between the fly ash particle and the catalyst surface, and the surface dif ⁇ fusion of the different atoms strongly increase with the temperature. At higher temperatures the overall mobility of the deactivating compounds is higher resulting in faster deactivation rates.
- the SCR catalyst is well distributed across the filter element wall.
- the fly ash gets collected under operation only on the outer filter surface.
- these are pre-treated with a dust powder which initially will fill the external open pores of the ceramic wall and then form a thin filter cake. From this moment on, all the dust present in the fluids that are passed through the filter element will accumulate on top of this filter cake and will not penetrate further into the filter wall.
- this pre-treatment when correctly done, can serve the purpose of protecting the catalyst present in the filter element against the alkali metals or alkali met- al compounds present, e.g. in fly ash formed in the combus ⁇ tion of biomass.
- the powder used in the pre- treatment must not react with the alkali metals or alkali metal compounds and thus do not favour their diffusion into the filter element wall.
- Such a powder should be alkaline in nature, e.g. calci ⁇ um/magnesium-based.
- the catalysed filters can be used in biomass applications and other ap ⁇ plications, where alkali metals or compounds thereof are contained in the flue gas in the temperature range 200-
- this invention provides a method of improving catalyst resistance in a catalysed fil ⁇ ter element against poisoning of the catalyst by alkali metals or alkali metal compounds, the method comprises af ⁇ fixing an alkaline powder on surface of the filter prior to the filter is brought into contact with the poisonous alka- li metals or alkali metal compounds.
- the protecting alkaline powder is affixed to the filters, while these are installed in the filter house by direct injection of the powder in the main duct upstream the filter house.
- the protecting powder may be affixed as a final step during production.
- the filters may be sold, installed and used without the need of pre- treatment on-site.
- Addition of the protecting powder to the filter element can be performed by wash-coating the filter element in a slurry containing the protecting powder.
- Suitable compounds and compositions for use in the protect ⁇ ing powder include talcum (Mg3Si40io (OH) 2) , calcium car ⁇ bonate, trisodium hydrogendicarbonate dehydrate
- the invention provides additionally a method for the prepa ⁇ ration of a catalysed filter being resistant against poi ⁇ soning by alkali metals or alkali metal compounds, compris ⁇ ing the step of affixing an alkaline powder on surface of the filter element.
- the alkaline powder affixed on surface of the filter ele ⁇ ment comprises preferably one or more of calcium/magnesium- based compounds, talcum and calcium carbonate, trisodium hydrogendicarbonate dehydrate (Na3 (C03) (HC03 ) ⁇ 2H20) , sodi ⁇ um bicarbonate and calcium hydroxide.
- the invention provides furthermore a method of cleaning flue gas containing alkali metals and/or alkali metal compounds comprising the step of affixing an alkaline powder on surface of a catalysed filter element prior to the catalysed filter element is brought into con ⁇ tact with the flue gas.
- the alkaline powder for use in the method comprises one or more of calcium/magnesium-based compounds, talcum and cal ⁇ cium carbonate.
- the method is in particular useful when applied to flue gas cleaning at temperatures above 200°C.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
A method and a catalysed filter element with improved alkali metal resistance for the removal of particulate matter and environmental or health harmful compounds from flue or off-gases containing alkali metals or alkali metal compounds wherein the filter element is pre-treated with an alkaline powder prior to operation.
Description
Title: Method and catalysed filter element with improved alkali-resistance for flue gas cleaning
The present invention is directed in general to the clean- ing of flue gases containing alkali metals or alkali metal compounds and to catalysed filter elements resistant against poisoning by alkali metals or alkali metal com¬ pounds. In particular, the invention provides a method and a catalysed filter element with improved alkali metal re- sistance filter elements for the removal of particulate matter and environmental or health harmful compounds from flue or off-gases containing alkali metals or alkali metal compounds . Deactivation of catalysts is fast, in particular SCR cata¬ lysts used in the treatment of flue gases from e.g. biomass combustion, waste incineration and glass manufacturing, which makes the use of these catalysts in these applica¬ tions rather challenging and economically disadvantageous. The deactivation is due to the alkali metals fraction of the fly ash contained in the flue gas that acts as a cata¬ lyst poison. In particular, the interaction between the alkali metals or alkali metal compounds and the active sites of the catalyst is facilitated by the fact that these alka- li metals are present in water soluble compounds and there¬ fore prone to "jump" from the ash particle onto the cata¬ lyst surface via acid-base reaction between the particle and the catalyst. Once on the surface, the alkali metals or alkali metal compounds further penetrate into the catalyst wall by surface diffusion, strongly bound to the catalyst active sites and deactivate the catalyst. The reaction be¬ tween the ash particle and the catalyst is due to the di-
rect physical contact between those two species facilitated by increasing temperatures. The deactivation rate of the catalyst is very fast at temperatures above 200°C. In fact, both the acid-base reaction taking place between the fly ash particle and the catalyst surface, and the surface dif¬ fusion of the different atoms strongly increase with the temperature. At higher temperatures the overall mobility of the deactivating compounds is higher resulting in faster deactivation rates.
In the case of catalysed filter elements, the SCR catalyst is well distributed across the filter element wall. The fly ash gets collected under operation only on the outer filter surface. In order to increase the surface filtration per- formance of the filters, these are pre-treated with a dust powder which initially will fill the external open pores of the ceramic wall and then form a thin filter cake. From this moment on, all the dust present in the fluids that are passed through the filter element will accumulate on top of this filter cake and will not penetrate further into the filter wall.
The above described pre-treatment is well known and used in industry for improving the filtration performance of the filters.
We have found that this pre-treatment, when correctly done, can serve the purpose of protecting the catalyst present in the filter element against the alkali metals or alkali met- al compounds present, e.g. in fly ash formed in the combus¬ tion of biomass.
In order to be effective, the powder used in the pre- treatment must not react with the alkali metals or alkali metal compounds and thus do not favour their diffusion into the filter element wall.
Such a powder should be alkaline in nature, e.g. calci¬ um/magnesium-based. With this pre-treatment , the catalysed filters can be used in biomass applications and other ap¬ plications, where alkali metals or compounds thereof are contained in the flue gas in the temperature range 200-
500°C without suffering the high rate of deactivation normally experienced with standard SCR catalysts.
Pursuant to the above findings, this invention provides a method of improving catalyst resistance in a catalysed fil¬ ter element against poisoning of the catalyst by alkali metals or alkali metal compounds, the method comprises af¬ fixing an alkaline powder on surface of the filter prior to the filter is brought into contact with the poisonous alka- li metals or alkali metal compounds.
In one embodiment of the invention, the protecting alkaline powder is affixed to the filters, while these are installed in the filter house by direct injection of the powder in the main duct upstream the filter house.
Alternatively, the protecting powder may be affixed as a final step during production. In this case the filters may be sold, installed and used without the need of pre- treatment on-site.
Addition of the protecting powder to the filter element can be performed by wash-coating the filter element in a slurry containing the protecting powder. Suitable compounds and compositions for use in the protect¬ ing powder include talcum (Mg3Si40io (OH) 2) , calcium car¬ bonate, trisodium hydrogendicarbonate dehydrate
(Na3 (C03) (HC03 ) · 2H20) , sodium bicarbonate and calcium hy¬ droxide .
The invention provides additionally a method for the prepa¬ ration of a catalysed filter being resistant against poi¬ soning by alkali metals or alkali metal compounds, compris¬ ing the step of affixing an alkaline powder on surface of the filter element.
The alkaline powder affixed on surface of the filter ele¬ ment comprises preferably one or more of calcium/magnesium- based compounds, talcum and calcium carbonate, trisodium hydrogendicarbonate dehydrate (Na3 (C03) (HC03 ) · 2H20) , sodi¬ um bicarbonate and calcium hydroxide.
As already mentioned hereinbefore, cleaning of flue gases containing alkali metals or alkali metal compounds by means of catalysed filters is problematic because of deactivation of the catalyst arranged on the filter by the alkali metals or compounds .
To solve this problem, the invention provides furthermore a method of cleaning flue gas containing alkali metals and/or alkali metal compounds comprising the step of affixing an alkaline powder on surface of a catalysed filter element
prior to the catalysed filter element is brought into con¬ tact with the flue gas.
The alkaline powder for use in the method comprises one or more of calcium/magnesium-based compounds, talcum and cal¬ cium carbonate.
The method is in particular useful when applied to flue gas cleaning at temperatures above 200°C.
Claims
1. A method of improving catalyst resistance of a cata¬ lysed filter element against poisoning by alkali metals or alkali metal compounds, the method comprises affixing an alkaline powder on surface of the filter element prior to the filter element is brought into contact with the poison¬ ous alkali metals or alkali metal compounds.
2. The method of claim 1, wherein the alkaline powder is affixed to the filter element by direct injection of the powder into a fluid to be filtered upstream the filter ele¬ ment .
3. The method of claim 1, wherein the alkaline powder is affixed during preparation of the filter element.
4. The method of claim 3, wherein the alkaline powder is affixed in form of a wash-coat.
5. The method of anyone of claims 1 to 4, wherein cata¬ lysed filter comprises a catalyst for the selective reduc¬ tion of nitrogen oxides.
6. The method according to anyone of the preceding claims, wherein the alkaline powder comprises one or more of calcium/magnesium-based compounds, talcum, calcium car¬ bonate, trisodium hydrogendicarbonate dehydrate
(Na3 (C03) (HC03 ) · 2H20) , sodium bicarbonate and calcium hy- droxide.
7. A method for the preparation of a catalysed filter be¬ ing resistant against poisoning by alkali metals or alkali metal compounds, comprising the step of affixing an alka¬ line powder on surface of the filter element.
8. The method of claim 7, wherein the alkaline powder comprises one or more of calcium/magnesium-based compounds, talcum, calcium carbonate, trisodium hydrogendicarbonate dehydrate (Na3 (C03) (HC03 ) · 2H20) , sodium bicarbonate and calcium hydroxide.
9. Use of the alkali metal resistant catalysed filter el¬ ement of claim 7 or 8 for cleaning flue gas from combustion of biomass, waste incineration and glass manufactory.
10. The use of claim 10, wherein the flue gas has a tem¬ perature of between 200 and 500°C.
11. A method of cleaning flue gas containing alkali metals and/or alkali metal compounds, comprising the step of af¬ fixing an alkaline powder on surface of a catalysed filter element prior to the catalysed filter element is brought into contact with the flue gas.
12. The method of claim 11, wherein the alkaline powder comprises one or more of calcium/magnesium-based compounds, talcum, calcium carbonate, trisodium hydrogendicarbonate dehydrate (Na3 (C03) (HC03 ) · 2H20) , sodium bicarbonate and calcium hydroxide.
13. The method of claim 11 or 12, wherein the flue gas has a temperature of between 200 and 500°C.
14. The method of anyone of claims 11 to 13, wherein the flue gas is formed by combustion of biomass, waste incin¬ eration or during manufacture of glass.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201270504 | 2012-08-24 | ||
| DKPA201270504 | 2012-08-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014029578A1 true WO2014029578A1 (en) | 2014-02-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2013/065577 WO2014029578A1 (en) | 2012-08-24 | 2013-07-24 | Method and catalyzed filter element with improved alkali-resistance for flue gas cleaning |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2014029578A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018172483A1 (en) | 2017-03-22 | 2018-09-27 | Assistance Publique - Hopitaux De Paris | Method for determining the potential efficacy of anticancer treatment |
| WO2020210553A1 (en) | 2019-04-09 | 2020-10-15 | Dermbiont, Inc. | Compositions and methods for improving skin health and for the treatment and prevention of diseases, disorders and conditions associated with pathogenic microbes |
| WO2022081762A1 (en) | 2020-10-14 | 2022-04-21 | Dermbiont, Inc. | Compositions and methods for improving skin health and for the treatment and prevention of diseases, disorders and conditions associated with fungi and other pathogenic microbes |
| WO2022178292A1 (en) | 2021-02-18 | 2022-08-25 | Vedanta Biosciences, Inc. | Compositions and methods for suppressing pathogenic organisms |
| WO2022216670A1 (en) | 2021-04-05 | 2022-10-13 | Vedanta Biosciences, Inc. | Compositions and methods for treating cancer |
| WO2023278477A1 (en) | 2021-06-28 | 2023-01-05 | Vedanta Biosciences, Inc. | Methods of colonizing a microbiome, treating and/or preventing inflammatory bowel disease and graft versus host disease |
| EP4282489A2 (en) | 2016-06-14 | 2023-11-29 | Vedanta Biosciences, Inc. | Treatment of clostridium difficile infection |
| EP4386090A1 (en) | 2022-12-12 | 2024-06-19 | Assistance Publique - Hôpitaux De Paris | Method for determining and improving the potential efficacy of anticancer treatment |
| EP4410954A2 (en) | 2017-12-11 | 2024-08-07 | Vedanta Biosciences, Inc. | Compositions and methods for suppressing pathogenic organisms |
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|---|---|---|---|---|
| EP0242488A1 (en) * | 1984-11-02 | 1987-10-28 | Mitsubishi Jukogyo Kabushiki Kaisha | Filter medium for treating an exhaust gas |
| US4786484A (en) * | 1987-02-03 | 1988-11-22 | Sanitech, Inc. | Process for absorbing toxic gas |
| US5051391A (en) * | 1988-04-08 | 1991-09-24 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst filter and method for manufacturing a catalyst filter for treating a combustion exhaust gas |
| US20030083197A1 (en) * | 2001-01-19 | 2003-05-01 | Naomi Noda | Catalyst element |
| WO2011073396A2 (en) * | 2009-12-18 | 2011-06-23 | Haldor Topsøe A/S | DEACTIVATION-RESISTANT CATALYST FOR SELECTIVE CATALYST REDUCTION OF NOx |
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2013
- 2013-07-24 WO PCT/EP2013/065577 patent/WO2014029578A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0242488A1 (en) * | 1984-11-02 | 1987-10-28 | Mitsubishi Jukogyo Kabushiki Kaisha | Filter medium for treating an exhaust gas |
| US4786484A (en) * | 1987-02-03 | 1988-11-22 | Sanitech, Inc. | Process for absorbing toxic gas |
| US5051391A (en) * | 1988-04-08 | 1991-09-24 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst filter and method for manufacturing a catalyst filter for treating a combustion exhaust gas |
| US20030083197A1 (en) * | 2001-01-19 | 2003-05-01 | Naomi Noda | Catalyst element |
| WO2011073396A2 (en) * | 2009-12-18 | 2011-06-23 | Haldor Topsøe A/S | DEACTIVATION-RESISTANT CATALYST FOR SELECTIVE CATALYST REDUCTION OF NOx |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4282489A2 (en) | 2016-06-14 | 2023-11-29 | Vedanta Biosciences, Inc. | Treatment of clostridium difficile infection |
| WO2018172483A1 (en) | 2017-03-22 | 2018-09-27 | Assistance Publique - Hopitaux De Paris | Method for determining the potential efficacy of anticancer treatment |
| EP4410954A2 (en) | 2017-12-11 | 2024-08-07 | Vedanta Biosciences, Inc. | Compositions and methods for suppressing pathogenic organisms |
| WO2020210553A1 (en) | 2019-04-09 | 2020-10-15 | Dermbiont, Inc. | Compositions and methods for improving skin health and for the treatment and prevention of diseases, disorders and conditions associated with pathogenic microbes |
| US11040077B2 (en) | 2019-04-09 | 2021-06-22 | Dermbiont, Inc. | Compositions and methods for improving skin health and for the treatment and prevention of diseases, disorders and conditions associated with pathogenic microbes |
| US12064459B2 (en) | 2019-04-09 | 2024-08-20 | Dermbiont, Inc. | Compositions and methods for improving skin health and for the treatment and prevention of diseases, disorders and conditions associated with pathogenic microbes |
| WO2022081762A1 (en) | 2020-10-14 | 2022-04-21 | Dermbiont, Inc. | Compositions and methods for improving skin health and for the treatment and prevention of diseases, disorders and conditions associated with fungi and other pathogenic microbes |
| WO2022178292A1 (en) | 2021-02-18 | 2022-08-25 | Vedanta Biosciences, Inc. | Compositions and methods for suppressing pathogenic organisms |
| WO2022216670A1 (en) | 2021-04-05 | 2022-10-13 | Vedanta Biosciences, Inc. | Compositions and methods for treating cancer |
| WO2023278477A1 (en) | 2021-06-28 | 2023-01-05 | Vedanta Biosciences, Inc. | Methods of colonizing a microbiome, treating and/or preventing inflammatory bowel disease and graft versus host disease |
| EP4386090A1 (en) | 2022-12-12 | 2024-06-19 | Assistance Publique - Hôpitaux De Paris | Method for determining and improving the potential efficacy of anticancer treatment |
| WO2024126391A1 (en) | 2022-12-12 | 2024-06-20 | Assistance Publique - Hopitaux De Paris | Method for determining and improving the potential efficacy of anticancer treatment |
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