WO2018158184A1 - Processus d'élimination d'oxydes de soufre et d'oxydes d'azote contenus dans un effluent gazeux d'une installation industrielle - Google Patents

Processus d'élimination d'oxydes de soufre et d'oxydes d'azote contenus dans un effluent gazeux d'une installation industrielle Download PDF

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Publication number
WO2018158184A1
WO2018158184A1 PCT/EP2018/054649 EP2018054649W WO2018158184A1 WO 2018158184 A1 WO2018158184 A1 WO 2018158184A1 EP 2018054649 W EP2018054649 W EP 2018054649W WO 2018158184 A1 WO2018158184 A1 WO 2018158184A1
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WO
WIPO (PCT)
Prior art keywords
gas
sulphur
filter bag
oxides
scr
Prior art date
Application number
PCT/EP2018/054649
Other languages
English (en)
Inventor
Joakim Reimer THØGERSEN
Francesco Castellino
Souheil SAADI
Niklas Bengt Jakobsson
Original Assignee
Haldor Topsøe A/S
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 Topsøe A/S filed Critical Haldor Topsøe A/S
Publication of WO2018158184A1 publication Critical patent/WO2018158184A1/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
    • B01D53/34—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
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • 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
    • B01D53/88—Handling or mounting catalysts
    • 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
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • 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
    • B01D2255/10—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
    • B01D2255/20707—Titanium
    • 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
    • B01D2255/20761—Copper
    • 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
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to a process for cleaning an off-gas containing sulphur oxides (SOx)and nitrogen oxides (NOx) employing removal of SOx and ammonia-SCR in a single filtration unit, in particular a filter bag house with one or more catalysed fabric filter assemblies.
  • Selective catalytic reduction (SCR) is primarily a means of converting nitrogen oxides (NOx) into 2 and H 2 0 by reac ⁇ tion with anhydrous ammonia or aqueous ammonia in presence of an SCR catalyst.
  • the NOx reduction reaction takes place as the gas contacts an SCR catalyst.
  • Ammonia, or a precursor, such as urea is injected and mixed with the gas upstream the SCR catalyst.
  • the typical SOx level in COG is 150 mg/Nm3 - 180 mg/Nm3.
  • COG and other SOx and NOx containing off-gases must be cleaned by removal of these impurities.
  • the bulk dew point of ammonium bisulphate at the SCR reac- tor inlet is typically around 290°C, but the observed dew point is higher due to capillary forces in the micropore structure of the SCR catalyst.
  • Certain SCR catalysts such as the vanadium-based cata ⁇ lysts, are particularly sensitive to contamination from ammonium sulphate and especially ammonium bisulphate, which is condensed in the pore structure of the catalyst at lower temperatures, thereby physically blocking the pores and de ⁇ activating the catalyst.
  • One way to avoid the off-gas cleaning below the dew point of ammonium bisulphate is to perform the SCR prior to cool- ing the gas.
  • this invention provides a Process for the removal sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant comprising the steps of
  • step (d) passing the off-gas solid mixture together with the am ⁇ monia nitrogen oxide reducing agent to a filter bag house; (e) in the filter bag house passing the ammonia nitrogen reducing agent containing off-gas solid mixture obtained in step (c) through one or more fabric filter assemblies and filtering off the sulphur oxides adsorbed on the pulverous sulphur oxide adsorbent on dispersion side of the one or more fabric filter bag assemblies; and
  • the process of the invention is in particular useful when main part of the sulphur oxides is SO 3 , as SO 3 reacts very fast with ammonia to ammonium bisulphate.
  • the off-gas is cooled by means of indirect heat-exchange in a heat exchanger, which typically is pre ⁇ sent in most of the existing cleaning systems for the re ⁇ moval of sulphur compounds. This makes the process accord ⁇ ing to the invention attractive for retrofit of these cleaning systems.
  • the filter bag house will contain a plurality of fabric filter bags assemblies arranged in usual manner in the house.
  • the filter bag assemblies may each consist of a single fab- ric filter bag with an SCR catalyst coated on fabric in the permeation side of the bag.
  • the filter bag assemblies each comprises an outer filter bag and one or more inner filter bags separately and concentrically arranged within the outer tubular filter bag.
  • outer filter bag refers to the filter bag through which the process gas passes first
  • inner filter bag refers to the filter bag(s) through which the process gas passes successively after having passed through the outer bag.
  • the later embodiment has the advantage that either differ ⁇ ent types and/or amounts of catalysts can be coated on dif ⁇ ferent filter bags in each filter bag assembly.
  • the SCR catalyst applied on the filter bags comprises vana ⁇ dium pentoxide and titanium oxide and optionally addition ⁇ ally oxides of tungsten and/or molybdenum.
  • the catalytically active material can further comprise pal ⁇ ladium or platinum in metallic and/or oxidic form.
  • These catalysts are active both in the removal of VOCs if present 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 sulphur-tolerant, and (iii) it has a lower SO 2 oxidation activity compared to other catalyst compositions .
  • the SCR catalyst comprises a mixture of oxides of manganese, cerium and iron supported on titania.
  • Such an SCR catalyst has a sufficient catalytic activity at temperatures well below 190°C, e.g. 130°C. Thereby, it is possible to remove or sufficiently reduce ammonia slip from the SCR catalyst at lower temperatures.
  • Sulphur oxide adsorbent particles present in the process gas will be deposited on the outer surface, i.e. the dis ⁇ persion side of the fabric filter bag facing the uncleaned off-gas solid mixture.
  • the catalysts loaded onto the outer bag and/or the inner bag(s) are effectively protected against potential catalyst poisons in particular sulphur oxides present in the off-gas.
  • SCR composition useful in the process according to the invention include compositions comprising one or more acidic zeolite or zeotype components selected from the group consisting of BEA, MFI, FAU, FER, CHA, MOR or mixtures thereof physically admixed with one or more redox ac ⁇ tive metal compounds selected from the group consisting of CU/AI 2 0 3 , Mn/Al 2 0 3 , Ce0 2 -Zr0 2 , Ce-Mn/Al 2 0 3 and mixtures thereof, as described in US patent 9,168,517.
  • the process according to the invention is well suited for the removal of sulphur com- pounds and prevents formation of ammonium bisulphate in off-gas from coke production and from regenerative oxida ⁇ tion processes with a sulphur containing fuel.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (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)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un processus de nettoyage d'un effluent gazeux contenant des oxydes de soufre (SOx) et des oxydes d'azote (NOx) utilisant l'élimination de SOx et d'ammoniac-SCR dans une seule unité de filtration, en particulier une maison à sac filtrant avec un ou plusieurs ensembles filtres en tissu catalysé.
PCT/EP2018/054649 2017-03-02 2018-02-26 Processus d'élimination d'oxydes de soufre et d'oxydes d'azote contenus dans un effluent gazeux d'une installation industrielle WO2018158184A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA201700148 2017-03-02
DKPA201700148 2017-03-02

Publications (1)

Publication Number Publication Date
WO2018158184A1 true WO2018158184A1 (fr) 2018-09-07

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PCT/EP2018/054649 WO2018158184A1 (fr) 2017-03-02 2018-02-26 Processus d'élimination d'oxydes de soufre et d'oxydes d'azote contenus dans un effluent gazeux d'une installation industrielle

Country Status (2)

Country Link
TW (1) TW201838707A (fr)
WO (1) WO2018158184A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109550348A (zh) * 2018-10-29 2019-04-02 中国石油天然气集团有限公司 稠油火驱采出气中不凝气的处理方法及装置
WO2022146872A1 (fr) * 2020-12-30 2022-07-07 W.L. Gore & Associates, Inc. Amélioration de l'efficacité catalytique de filtration de gaz de combustion par formation de sel à l'aide d'au moins un agent oxydant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4220633A (en) * 1979-04-30 1980-09-02 The Babcock & Wilcox Company Filter house and method for simultaneously removing NOx and particulate matter from a gas stream
EP0268353A1 (fr) * 1986-11-19 1988-05-25 The Babcock & Wilcox Company Contrôle du dégagement des produits polluants d'une chaudière à charbon
US5540897A (en) * 1988-07-25 1996-07-30 The Babcock & Wilcox Company Improved SOx, NOx, and particulate removal system
WO2006103040A1 (fr) * 2005-04-01 2006-10-05 Haldor Topsøe A/S Procede de reduction catalytique de nox au moyen d'ammoniac en presence de so3 contenu dans le gaz
WO2015140305A1 (fr) * 2014-03-21 2015-09-24 Haldor Topsøe A/S Ensemble filtre à manches
US9168517B2 (en) 2011-10-24 2015-10-27 Haldor Topsoe A/S Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides
CN104190193B (zh) * 2014-08-22 2015-11-18 合肥工业大学 一种袋式除尘器内同步脱硫脱硝除尘的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4220633A (en) * 1979-04-30 1980-09-02 The Babcock & Wilcox Company Filter house and method for simultaneously removing NOx and particulate matter from a gas stream
EP0268353A1 (fr) * 1986-11-19 1988-05-25 The Babcock & Wilcox Company Contrôle du dégagement des produits polluants d'une chaudière à charbon
US5540897A (en) * 1988-07-25 1996-07-30 The Babcock & Wilcox Company Improved SOx, NOx, and particulate removal system
WO2006103040A1 (fr) * 2005-04-01 2006-10-05 Haldor Topsøe A/S Procede de reduction catalytique de nox au moyen d'ammoniac en presence de so3 contenu dans le gaz
US9168517B2 (en) 2011-10-24 2015-10-27 Haldor Topsoe A/S Catalyst composition and method for use in selective catalytic reduction of nitrogen oxides
WO2015140305A1 (fr) * 2014-03-21 2015-09-24 Haldor Topsøe A/S Ensemble filtre à manches
CN104190193B (zh) * 2014-08-22 2015-11-18 合肥工业大学 一种袋式除尘器内同步脱硫脱硝除尘的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109550348A (zh) * 2018-10-29 2019-04-02 中国石油天然气集团有限公司 稠油火驱采出气中不凝气的处理方法及装置
WO2022146872A1 (fr) * 2020-12-30 2022-07-07 W.L. Gore & Associates, Inc. Amélioration de l'efficacité catalytique de filtration de gaz de combustion par formation de sel à l'aide d'au moins un agent oxydant

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Publication number Publication date
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