WO1997040922A1 - Procede d'adsorption d'hydrocarbures provenant de gaz brules - Google Patents

Procede d'adsorption d'hydrocarbures provenant de gaz brules Download PDF

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Publication number
WO1997040922A1
WO1997040922A1 PCT/EP1997/002147 EP9702147W WO9740922A1 WO 1997040922 A1 WO1997040922 A1 WO 1997040922A1 EP 9702147 W EP9702147 W EP 9702147W WO 9740922 A1 WO9740922 A1 WO 9740922A1
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WO
WIPO (PCT)
Prior art keywords
hydrocarbons
adsorbent
exhaust gas
fluidized bed
via line
Prior art date
Application number
PCT/EP1997/002147
Other languages
German (de)
English (en)
Inventor
Günter BOENING
Jochim Eschenburg
Hansjörg Herden
Original Assignee
Metallgesellschaft Aktiengesellschaft
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 Metallgesellschaft Aktiengesellschaft filed Critical Metallgesellschaft Aktiengesellschaft
Publication of WO1997040922A1 publication Critical patent/WO1997040922A1/fr

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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
    • B01D53/02—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
    • B01D53/06—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 with moving adsorbents, e.g. rotating beds
    • B01D53/10—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 with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter

Definitions

  • the invention relates to a process for the adsorption of at industrial combustion processes using hydrocarbon-containing materials occurring saturated and aromatic hydrocarbons (BTX aromatics) microns containing oxygen-containing flue gases of mineral adsorbent having an average grain size d of 5 to 50, in which the a temperature of 80 to 180 ° C and one
  • BTX aromatics saturated and aromatic hydrocarbons
  • Flow rate of 3 to 20 m / s containing flue gases for a period of 0.5 to 100 s with adsorbent in a flue gas adsorbent suspension with an average density of 0.02 to 10 kg adsorbent / Nm 3 flue gas are brought into contact.
  • Combustion plants, incinerators for waste, sewage sludge or the like generally use materials that are burned in the presence of oxygen.
  • the resulting oxygen-containing smoke gases have a Concentration of up to 800 mg saturated and aromatic hydrocarbons per Nm 3 of flue gas. Since such substances may have a carcinogenic effect on the environment, according to "1.
  • DE-A-4012982 discloses a process for purifying gases and exhaust gases from inorganic and organic pollutants, in which finely powdered, activated aluminum oxide, silica gel, diatomaceous earth, finely powdered zeolites and / or similar inorganic substances are blown into the gas stream, gas and solid mixed, the solids applied to a surface filter, left as a renewable, loose, sufficiently deep adsorption layer on the filter and the solids are mechanically loaded with pollutants from there, removed.
  • DE-A-4403244 describes that the heavy metals and the heavy metal compounds, especially mercury and mercury compounds, as well as polyhalogenated hydrocarbons are present in combustion gases in a lower concentration. These substances have an extremely toxic effect and must therefore be removed almost quantitatively from the exhaust gases, which according to the prior art is preferably carried out by adsorption processes and / or washing processes. Activated carbon and zeolites have proven particularly useful as adsorbents, while the washing processes work both in the acidic and in the alkaline range.
  • the subject of DE-A-4403244 is a process for the purification of oxygen-containing waste gases resulting from the incineration of waste, industrial waste and sewage sludge, in which mercury, mercury compounds and polyhalogenated hydrocarbons are removed from the waste gases by adsorption on zeolites.
  • the exhaust gases above the dew point at a temperature of 80 to 180 ° C and a gas velocity of 3 to 20 m / s with a mixture of naturally occurring zeolites during a reaction time of 0.5 to 10 s in a gas-solid suspension brought to reaction.
  • the average particle size d as the zeolite mixture is 5 to 10 kg to 50 microns and the average suspension density of the gas-solids suspension 0.02 of solids per Nm 3 exhaust gas.
  • Carbon molecular sieves, activated carbon or the like are not suitable because of their flammability in the temperature range mentioned above.
  • the object of the present invention is therefore to remove saturated and aromatic hydrocarbons from flue gas, in particular the exhaust gas of a cement kiln, with suitable mineral adsorbents and to feed them back to the combustion process.
  • the adsorption and desorption of the hydrocarbons are expediently each in a fluidized bed, preferably a circulating fluidized bed, at a speed of 0.5 to 8 m / s and an average density of the hydrocarbons
  • the circulating fluidized bed is designed as a circulation system which consists of a reactor, a solids separator and a solids return line. It is characterized in that, in contrast to the classic fluidized bed, in which a dense phase is separated from the gas space above by a clear density jump, there are distribution states without a defined boundary layer. A leap in density between the dense phase and the gas space above it does not exist with a circulating fluidized bed; however, the solids concentration within the reactor decreases continuously from bottom to top.
  • the operating conditions of a circulating fluidized bed are as is known to be determined by the key figures of Froude and Archimedes.
  • the adsorption and desorption of the hydrocarbons each in an entrained flow reactor at a speed of 6 to 20 m / s and an average density of the flue gas adsorbent suspension of 0.2 to 200 g of solid / Nm 3 flue gas can be carried out.
  • the advantages achieved by the invention are, in particular, that not only the concentration of saturated and aromatic hydrocarbons is reduced to significantly below 5 mg / Nm 3 of flue gas, but also a combination of this method with known methods for removing other pollutants from flue gases can be combined.
  • the hydrocarbons obtained in the process according to the invention can be returned to the incineration plant.
  • FIGS. 1 and 2 the method designed according to the invention is shown as an example as a flow chart in FIGS. 1 and 2 and is explained in more detail below.
  • flue gas with a temperature of approx. 800 ° C. and a BTX aromatics content of> 5 mg / Nm 3 emerges from the boiler (1), which is charged with coal via line (2), and becomes About the heat exchanger (3) in which the temperature of the flue gas is reduced to about 200 ° C, and line (4) to the electrostatic precipitator (5), in which extensive dedusting of the flue gas takes place. That a temperature of approx Flue gas having 150 ° C. then flows into the fluidized bed reactor (7) via line (6). Via line (8) the incoming flue gas is natural zeolite as an adsorbent or a zeolite mixture having an average grain size d as from 10 to 20 .mu.m added.
  • a gas-solid suspension is generated in the fluidized bed reactor (7), which is in the state of a circulating fluidized bed with an average suspension density of 40 g / Nm 3 .
  • the fluidized bed reactor (7) there is a larger amount of zeolite, a small part of which is continuously fed via line (9) to a cyclone (10) in which the zeolite is separated from the cleaned flue gas and partly via line (11) fed back into the fluidized bed reactor (7) and the other part is fed via line (12) into the eddy current reactor (13).
  • the zeolite loaded with BTX hydrocarbon is desorbed at a temperature of approx. 400 ° C.
  • Pre-heated combustion air flows into the fluidized bed reactor (13) via line (14) to a temperature of 400 ° C. in the heat exchanger (3).
  • the combustion air loaded with BTX aromatics has a temperature of 380 ° C and is fed from the fluidized bed reactor (13) via line (15) to a cyclone (16) in which the zeolites are separated from the combustion air loaded with BTX aromatics.
  • the combustion air flows into the boiler (1) via line (17).
  • a part of the zeolite discharged from the cyclone (13) is returned to the fluidized bed reactor (13) via line (18).
  • the other part of the desorbed zeolite is returned to the fluidized bed reactor (7) via line (19).
  • a small part of this zeolite is removed from the process via line (20). That from the cyclone (10) via line (21) escaping cleaned flue gas is discharged to the chimney, not shown.
  • a rotary kiln (22) air via line (23), coal via line (24) and limestone via line (25).
  • the smoke gases laden with hydrocarbons which have a temperature of 350 ° C. and leave the rotary kiln (22) via line (20), are cleaned of dust particles in the electrostatic precipitator system (27) at a temperature of approximately 180 ° C.
  • the cleaned flue gases are fed via line (28) to the fluidized bed reactor (29) with a circulating fluidized bed.
  • Natural zeolite with an average grain size d 50 of approx. 25 ⁇ m is added to the inflowing flue gas via line (30).
  • a gas-solid suspension is formed which has an average suspension density of approximately 3 kg of solid per Nm 3 of flue gas.
  • a certain amount of hydrocarbon-laden zeolite is continuously fed to a cyclone (32) via line (31).
  • the cleaned exhaust gas flows via line (33) into the chimney, not shown.
  • the zeolite discharged from the cyclone (32) is partly returned to the fluidized bed reactor (29) via line (34), partly fed to the rotary kiln (22) via line (35) and partly passed to the fluidized bed reactor (37) via line (36) .
  • the zeolites loaded with hydrocarbons are desorbed at a temperature of approximately 400 ° C.
  • Preheated combustion air derived from the rotary kiln (22) via line (38) is used as the medium suitable for desorption.
  • the combustion air loaded with hydrocarbons leaves the fluidized bed reactor (37) via line (39) and flows into the Cyclone (40) in which the reactivated zeolite is deposited.
  • the reactivated zeolite is returned via line (41) to the fluidized bed reactor (32) and only a small part is removed from the process process via line (42).
  • the combustion air laden with hydrocarbons leaves the cyclone (40) via line (43) and flows into the rotary kiln (22).

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé d'adsorption de gaz brûlés contenant des hydrocarbures produits lors de processus de combustion faisant appel à des matériaux contenant des hydrocarbures. Selon ce procédé, un adsorbant minéral à grain fin est mis en contact avec les gaz brûlés dans une suspension gaz brûlés-adsorbant. Pour ramener les hydrocarbures dans le processus de combustion, l'adsorbant est soumis à un traitement thermique pour provoquer une désorption thermique des hydrocarbures.
PCT/EP1997/002147 1996-04-29 1997-04-25 Procede d'adsorption d'hydrocarbures provenant de gaz brules WO1997040922A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19617076.1 1996-04-29
DE1996117076 DE19617076A1 (de) 1996-04-29 1996-04-29 Verfahren zur Adsorption von Kohlenwasserstoffen aus Rauchgasen

Publications (1)

Publication Number Publication Date
WO1997040922A1 true WO1997040922A1 (fr) 1997-11-06

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ID=7792764

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/002147 WO1997040922A1 (fr) 1996-04-29 1997-04-25 Procede d'adsorption d'hydrocarbures provenant de gaz brules

Country Status (2)

Country Link
DE (1) DE19617076A1 (fr)
WO (1) WO1997040922A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5515657A (en) * 1978-07-21 1980-02-02 Mitsubishi Heavy Ind Ltd Method of removing mal-odorous component in exhaust gas
EP0455152A1 (fr) * 1990-04-28 1991-11-06 Deutsche Babcock Anlagen Gmbh Procédé pour la purification des effluents gazeux
DE4128106A1 (de) * 1991-08-24 1993-02-25 Metallgesellschaft Ag Verfahren zur abtrennung von hochkondensierten, polyzyklischen kohlenwasserstoffen aus abgasen
EP0529661A2 (fr) * 1991-08-30 1993-03-03 Chiyoda Corporation Procédé et dispositif pour la séparation de gaz
EP0666098A2 (fr) * 1994-02-03 1995-08-09 Metallgesellschaft Ag Procédé pour la purification de gaz de combustion
DE4415719A1 (de) * 1994-05-04 1995-11-09 Metallgesellschaft Ag Verfahren zur Abgasreinigung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3919124A1 (de) * 1989-06-12 1990-01-18 Haji Javad Mehdi Dr Ing Verfahren zur abscheidung von polyzylkischen kohlenwasserstoffen und schwermetallen aus abgasen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5515657A (en) * 1978-07-21 1980-02-02 Mitsubishi Heavy Ind Ltd Method of removing mal-odorous component in exhaust gas
EP0455152A1 (fr) * 1990-04-28 1991-11-06 Deutsche Babcock Anlagen Gmbh Procédé pour la purification des effluents gazeux
DE4128106A1 (de) * 1991-08-24 1993-02-25 Metallgesellschaft Ag Verfahren zur abtrennung von hochkondensierten, polyzyklischen kohlenwasserstoffen aus abgasen
EP0529661A2 (fr) * 1991-08-30 1993-03-03 Chiyoda Corporation Procédé et dispositif pour la séparation de gaz
EP0666098A2 (fr) * 1994-02-03 1995-08-09 Metallgesellschaft Ag Procédé pour la purification de gaz de combustion
DE4415719A1 (de) * 1994-05-04 1995-11-09 Metallgesellschaft Ag Verfahren zur Abgasreinigung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8011, Derwent World Patents Index; Class E19, AN 80-19313C, XP002018332 *

Also Published As

Publication number Publication date
DE19617076A1 (de) 1997-11-06

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