WO2000062906A1 - Method and device for exhaust gas cleaning - Google Patents

Method and device for exhaust gas cleaning Download PDF

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Publication number
WO2000062906A1
WO2000062906A1 PCT/CH2000/000211 CH0000211W WO0062906A1 WO 2000062906 A1 WO2000062906 A1 WO 2000062906A1 CH 0000211 W CH0000211 W CH 0000211W WO 0062906 A1 WO0062906 A1 WO 0062906A1
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Prior art keywords
oxide
metal
exhaust gases
mercury
channels
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PCT/CH2000/000211
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German (de)
French (fr)
Inventor
Jürg WEGMANN
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Frick, Martin
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Priority to AU35486/00A priority Critical patent/AU3548600A/en
Publication of WO2000062906A1 publication Critical patent/WO2000062906A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B43/00—Obtaining mercury
    • 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
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/322—Basic shape of the elements
    • B01J2219/32296—Honeycombs
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/324—Composition or microstructure of the elements
    • B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2219/00—Treatment devices
    • F23J2219/10—Catalytic reduction devices

Definitions

  • the invention relates to a method and a device according to the preambles of the corresponding claims.
  • the method and device are used to purify exhaust gases, in particular to remove mercury, for example from exhaust gases from incineration plants (e.g. waste incineration plants, hospital waste incineration plants, waste wood incineration plants, crematoriums or also explosive disposal plants) or from production exhaust air.
  • incineration plants e.g. waste incineration plants, hospital waste incineration plants, waste wood incineration plants, crematoriums or also explosive disposal plants
  • production exhaust air e.g. waste incineration plants, hospital waste incineration plants, waste wood incineration plants, crematoriums or also explosive disposal plants
  • Mercury is partly present in vapor form in the exhaust gases mentioned or deposited as metal on solid particles and, because of its toxicity, is a high burden on the environment. For this reason, attempts are made to remove mercury from these exhaust gases as quantitatively as possible.
  • the object of the invention is to provide a method and a device for exhaust gas purification, in particular for removing mercury from combustion exhaust gases, which compared to corresponding methods and devices according to the prior art have an increased cleaning performance, a simpler regeneration and a larger one Allow range of application in terms of temperature.
  • the method according to the invention consists in flowing the exhaust gases in a flow which is as homogeneous and straight as possible over a surface coated with a metal oxide or a mixed metal oxide, the metal whose oxide is used for the coating being a metal which forms an amalgam with mercury .
  • Mercury which is vaporized in the exhaust gas, is absorbed to a high percentage in the coated surface if the surface is designed in such a way that the gas particles in the flow collide with the surface approximately twice on average.
  • the absorption of mercury in such surfaces is possible at temperatures up to approx. 120 ° C. It can be seen that a metal oxide coating with a thickness in the range of 2 to 10 ⁇ m can be loaded with mercury in a weight ratio of up to approx.
  • regenerate the metal oxide surfaces used they are heated at temperatures of approximately 150 to 160 ° C., for example in an oven, with hot gas flowing through the oven.
  • the furnace exhaust gases are cooled and the pollutants are pure substances.
  • the cleaned surfaces can then be regenerated with e.g. Subjected to hydrogen and then reused.
  • the device according to the invention has at least one channel, preferably a plurality of channels, the walls of which are coated with a metal oxide and which are arranged in a housing with gas inlet and gas outlet for integration into an exhaust gas channel.
  • FIGS. 1 and 2 show an exemplary embodiment of the device according to the invention.
  • This has a housing 1 with gas inlet E and gas outlet A.
  • At least one filler 2 is arranged in the housing 1 and divides the interior of the housing into a plurality of straight channels 3 running between gas inlet E and gas outlet A.
  • the housing contains, as shown in the flow direction, spaces for five fillers, with fillers being arranged, for example, in three of the spaces, depending on the amount of mercury, and two reserve spaces being provided.
  • the packing elements are spaced apart from one another in such a way that turbulence forms between the packing elements when flowing through.
  • the filler body 2 is made, for example, from structured metal sheets (for example from stainless steel foils) or it is an extruded ceramic body made from, for example, cordierite, as is known from catalyst technology.
  • the channels are advantageously designed such that the exhaust gas flows through them in a flow that is as laminar as possible. This prevents deposits of solid particles in the channels, so that the active surfaces are not contaminated and thus maintain their absorption capacity up to a maximum load.
  • the channels are designed in such a way that a gas velocity in the range of 2 to 3 m / s results. It has been shown that fillers are advantageously used, the rectilinear channels of which have a cross section in the range from 20 to 50 mm 2 (for example a square cross section of 5 x 5 mm) and a length of 0.3 to 2 m (for example one to five fillers) 30 cm long) and in which all through the flowing gas towers on average about two times against the canal walls.
  • the coating of the channel walls consists of a metal oxide or mixed metal oxide, the metals being selected from the group which form amalgams with mercury.
  • a noble metal oxide e.g. Silver oxide is used or a mixed oxide of two noble metals or one noble metal and another metal, e.g. Silver / copper oxide.
  • the coating consists of a silver / copper oxide with a silver / copper ratio of 1: 5 to 1:10.
  • the packings 2 are made of metal sheets or metal foils, such as stainless steel sheets, it is advantageous that MetaUober lake that form the inner surfaces of the channels, prior to coating with the said oxides to increase the surface first 'oxide with Alumim or coat titanium oxide.
  • Coating with copper / silver oxide is achieved, for example, by pretreating the stainless steel foils to be coated with oxalic acid, by wetting the pretreated surfaces with a solution of the corresponding metal oxalates (e.g. copper and silver oxalate) and by subsequently tempering the wetted surfaces in a hydrogen atmosphere .
  • a solution of the corresponding metal oxalates e.g. copper and silver oxalate
  • the resulting layers have a thickness of approximately 5 to 10 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)

Abstract

Mercury is removed for exhaust gases by passing the gases over surfaces coated with an oxide of at least one metal forming an amalgam with mercury. A corresponding waste gas cleaning device comprises a housing (1) with a gas inlet (E) and a gas outlet (A), at least a filling body (2) being disposed in said housing (1) that divides the inner space of the housing (1) into a plurality of channels (3) between the gas inlet and the gas outlet, wherein at least the inner surfaces of the channels (3) are coated with the above-mentioned oxide. At a coating density in the order of 5 to 10 νm, the device can be charged without undergoing any performance loss, the oxide coating-to-mercury charge ratio being approximately 1:1. The method and the device can be used in waste gas temperatures of approximately 120° C. The device can be regenerated by means of treatment at temperatures ranging approximately from 150 to 160° C. The method and the device can be used, for instance, for cleaning crematorium waste gases.

Description

VERFAHREN UND VORRICHTUNG ZUR REINIGUNG VON ABGASEN METHOD AND DEVICE FOR PURIFYING EXHAUST GAS
Die Erfindung betrifft ein Verfahren und eine Vorrichtung nach den Oberbegriffen der entsprechenden Patentansprüche. Verfahren und Vorrichtung dienen zur Reinigung von Abgasen, insbesondere zum Entfernen von Quecksilber, beispielsweise aus Abgasen von Verbrennungsanlagen (z.B. Kehricht- verbrenmingsanlagen, Klinikmüll- Verbrennungsanlagen, -Altholz- Verbrennungsanlagen, Krematorien oder auch Sprengstoffbeseitigungsanlagen) oder aus Produktionsablüften.The invention relates to a method and a device according to the preambles of the corresponding claims. The method and device are used to purify exhaust gases, in particular to remove mercury, for example from exhaust gases from incineration plants (e.g. waste incineration plants, hospital waste incineration plants, waste wood incineration plants, crematoriums or also explosive disposal plants) or from production exhaust air.
Quecksilber ist in den genannten Abgasen teils dampfförmig oder als Metall an Festkörperteilchen angelagert vorhanden und stellt wegen seiner Giftigkeit eine hohe Belastung der Umwelt dar. Aus diesem Grunde wird versucht, Quecksilber möglichst quantitativ aus diesen Abgasen zu entfernen.Mercury is partly present in vapor form in the exhaust gases mentioned or deposited as metal on solid particles and, because of its toxicity, is a high burden on the environment. For this reason, attempts are made to remove mercury from these exhaust gases as quantitatively as possible.
Es ist bekannt, Quecksilber zusammen mit anderen unerwünschten Bestandteilen, die in Abgasen in gas- oder dampfförmigem Zustand vorhanden sind, aus diesen zu entfernen dadurch, dass die Abgase durch einen Festbettadsor- ber aus Aktivkohle geleitet werden, wobei die Stoffe an der Aktivkohle ad- sorbiert und dadurch aus dem Abgas entfernt werden. Nachteile derartiger Aktivkohle-Festbetten zur Abgasreinigung sind die durch Kanalbildung redu- zierte Adsorbtion (nur ca. 20% des theoretischen Adsorbtionsvermögens), die nur beschränkt mögliche Regenerierbarkeit der Aktivkohle, die negative Beeinflussung des Festbettes durch im Abgas mitgeführte feste Partikel und die gegen oben beschränkte Temperatur, bei der Aktivkohle einsetzbar ist (maxi- mal ca. 60°C).It is known to remove mercury together with other undesirable constituents which are present in exhaust gases in the gaseous or vaporous state by passing the exhaust gases through a fixed bed adsorber made of activated carbon, the substances adhering to the activated carbon. sorbed and thereby removed from the exhaust gas. Disadvantages of such activated carbon fixed beds for exhaust gas purification are those reduced by channel formation. grained adsorption (only approx. 20% of the theoretical adsorption capacity), the limited possibility of regenerating the activated carbon, the negative influence of the fixed bed by solid particles carried in the exhaust gas and the temperature restricted to above, at which activated carbon can be used (maximum approx. 60 ° C).
Die Erfindung stellt sich die Aufgabe, ein Verfahren und eine Vorrichtung zur Abgasreinigung, insbesondere zum Entfernen von Quecksilber aus Verbren- nungsabgasen aufzuzeigen, die verglichen mit entsprechenden Verfahren und Vorrichtungen gemäss dem Stande der Technik eine erhöhte Reinigungslei- stung, eine einfachere Regenerierung und einen grösseren Anwendungsbereich bezüglich Temperatur erlauben.The object of the invention is to provide a method and a device for exhaust gas purification, in particular for removing mercury from combustion exhaust gases, which compared to corresponding methods and devices according to the prior art have an increased cleaning performance, a simpler regeneration and a larger one Allow range of application in terms of temperature.
Diese Aufgabe wird gelöst durch das Verfahren und die Vorrichtung, wie sie in den entsprechenden, unabhängigen Ansprüchen definiert sind.This object is achieved by the method and the device as defined in the corresponding independent claims.
Das erfindungsgemässe Verfahren besteht darin, die Abgase in einer möglichst homogenen und geradlinigen Strömung über eine mit einem Metalloxid oder einem Metallmischoxid beschichtete Oberfläche strömen zu lassen, wobei das Metall dessen Oxid für die Beschichtung verwendet wird, ein Metall ist, das mit Quecksilber ein Amalgam bildet. Quecksilber, das dampfförmig im Abgas -aufgeführt wird, wird zu einem hohen Prozentsatz in der beschichteten Oberfläche absorbiert, wenn die Oberfläche derart ausgelegt ist, dass die Gasteilchen in der Strömung im Mittel ca. zwei Mal mit der Oberfläche kollidieren. Die Absorption von Quecksilber in derartigen Oberflächen ist möglich bei Temperaturen bis zu ca. 120°C. Es zeigt sich, dass sich eine Metalloxid-Beschichtung mit einer Dicke im Bereiche von 2 bis 10 μm in einem Gewichtsverhältnis bis ca. 1 : 1 (1kg absorbiertes Quecksilber pro 1kg Beschichtungsmaterial) mit Quecksilber beladen lassen, ohne dass die Reinigungs-Leistung nachlässt. Es zeigt sich auch, dass bei einer möghchst homogenen und geradlinigen Strömung die Leistungsfähigkeit der Absorption nicht geschmälert wird durch in den Abgasen mitgeführte Staub-, Russ- oder Aschepartikel, dass es also nicht notwendig ist, derartige Partikel vor der Quecksilberabscheidung aus dem Abgas zu entfernen.The method according to the invention consists in flowing the exhaust gases in a flow which is as homogeneous and straight as possible over a surface coated with a metal oxide or a mixed metal oxide, the metal whose oxide is used for the coating being a metal which forms an amalgam with mercury . Mercury, which is vaporized in the exhaust gas, is absorbed to a high percentage in the coated surface if the surface is designed in such a way that the gas particles in the flow collide with the surface approximately twice on average. The absorption of mercury in such surfaces is possible at temperatures up to approx. 120 ° C. It can be seen that a metal oxide coating with a thickness in the range of 2 to 10 μm can be loaded with mercury in a weight ratio of up to approx. 1: 1 (1 kg of absorbed mercury per 1 kg of coating material) without the cleaning performance deteriorating. It also shows that with a flow that is as homogeneous and straight as possible, the efficiency of the absorption is not reduced by dust, soot or ash particles carried in the exhaust gases, so that it is not necessary to remove such particles from the exhaust gas before the mercury separation .
Zur Regeneration der verwendeten Metalloxid-Oberflächen werden diese bei Temperaturen von ca. 150 bis 160°C beispielsweise in einem Ofen aufgeheizt, wobei der Ofen mit Heissgas durchströmt wird. Die Ofenabgase werden ge- kühlt und die Schadstoffe fallen Reinstoffe an. Die gereinigten Oberflächen können dann einer Regeneration mit z.B. Wasserstoff unterzogen und dann wieder verwendet werden.To regenerate the metal oxide surfaces used, they are heated at temperatures of approximately 150 to 160 ° C., for example in an oven, with hot gas flowing through the oven. The furnace exhaust gases are cooled and the pollutants are pure substances. The cleaned surfaces can then be regenerated with e.g. Subjected to hydrogen and then reused.
Die erfindungsgemässe Vorrichtung weist mindestens einem Kanal auf, vorzugsweise eine Vielzahl von Kanälen, deren Wandungen mit einem Metalloxid beschichtet sind und die für eine Integration in einen Abgaskanal in einem Gehäuse mit Gaseinlass und Gasauslass angeordnet sind.The device according to the invention has at least one channel, preferably a plurality of channels, the walls of which are coated with a metal oxide and which are arranged in a housing with gas inlet and gas outlet for integration into an exhaust gas channel.
Eine beispielhafte Ausführungsform der erfindungsgemässen Vorrichtung wird anhand der folgenden Figuren im Detail beschrieben. Dabei zeigen:An exemplary embodiment of the device according to the invention is described in detail with reference to the following figures. Show:
Figuren 1 und 2 Schnitte durch eine beispielhafte Ausführung der erfindungs- gemässen Vorrichtung (Figur 1: Schnitt parallel zur Strömungsrichtung; Figur 2: Schnitt quer zur Strömungsrichtung). Die Figuren 1 und 2 zeigen eine beispielhafte Ausführungsform der erfin- dungsgemässen Vorrichtung. Diese weist ein Gehäuse 1 mit Gaseinlass E und Gasauslass A auf. Im Gehäuse 1 ist mindestens ein Füllkörper 2 angeordnet, der den Gehäuseinnenraum in ein Mehrzahl zwischen Gaseinlass E und Gas- auslass A verlaufende, geradlinige Kanäle 3 aufteilt. Das Gehäuse enthält beispielsweise, wie dargestellt in Strömungsrichtung Plätze für fünf Füllkörper, wobei je nach Quecksilberanfall beispielsweise an drei der Plätze Füllkörper angeordnet sind und zwei Reserveplätze vorgesehen sind. Für eine Verbesserung der Wirkung sind die Füllkörper voneinander beabstandet, derart, dass bei der Durchströmung zwischen den Füllkörpern Verwirbelungen bilden.Figures 1 and 2 sections through an exemplary embodiment of the device according to the invention (Figure 1: section parallel to the flow direction; Figure 2: section transverse to the flow direction). FIGS. 1 and 2 show an exemplary embodiment of the device according to the invention. This has a housing 1 with gas inlet E and gas outlet A. At least one filler 2 is arranged in the housing 1 and divides the interior of the housing into a plurality of straight channels 3 running between gas inlet E and gas outlet A. For example, the housing contains, as shown in the flow direction, spaces for five fillers, with fillers being arranged, for example, in three of the spaces, depending on the amount of mercury, and two reserve spaces being provided. In order to improve the effect, the packing elements are spaced apart from one another in such a way that turbulence forms between the packing elements when flowing through.
Der Füllkörper 2 ist beispielsweise aus strukturierten Blechen (z.B. aus Edel- stahlfolien) gefertigt oder es handelt sich um einen extrudierten Keramikkör- per aus beispielsweise Cordierit, wie er aus der Katalysatortechnik bekannt ist.The filler body 2 is made, for example, from structured metal sheets (for example from stainless steel foils) or it is an extruded ceramic body made from, for example, cordierite, as is known from catalyst technology.
Die Kanäle sind vorteilhafterweise derart ausgelegt, dass das Abgas sie in einer möglichst laminaren Strömung durchströmt. Damit werden Ablagerungen von Festkörperpartikel in den Kanälen verhindert, sodass die aktiven Oberflächen nicht verschmutzt werden und dadurch ihre Absorptionsfähigkeit bis zu einer maximalen Beladung beibehalten.The channels are advantageously designed such that the exhaust gas flows through them in a flow that is as laminar as possible. This prevents deposits of solid particles in the channels, so that the active surfaces are not contaminated and thus maintain their absorption capacity up to a maximum load.
Gute Resultate werden erzeugt, wenn die Kanäle derart ausgelegt sind, dass sich eine Gasgeschwindigkeit im Bereiche von 2 bis 3 m/s ergibt. Es zeigt sich, dass vorteilhafterweise Füllkörper angewendet werden, deren geradlinig verlaufende Kanäle eine Querschnitt im Bereiche von 20 bis 50 mm2 (z.B. quadratischer Querschnitt von 5 x 5 mm) und eine Länge von 0,3 bis 2 m (z.B. ein bis fünf Füllkörper von 30 cm Länge) haben und in denen alle durchströmenden Gasteüchen im Schnitt etwa zwei mal an die Kanalwandun- gen stossen.Good results are achieved if the channels are designed in such a way that a gas velocity in the range of 2 to 3 m / s results. It has been shown that fillers are advantageously used, the rectilinear channels of which have a cross section in the range from 20 to 50 mm 2 (for example a square cross section of 5 x 5 mm) and a length of 0.3 to 2 m (for example one to five fillers) 30 cm long) and in which all through the flowing gas towers on average about two times against the canal walls.
Die Beschichtung der Kanalwände besteht aus einem Metalloxid oder Metall- mischoxid, wobei die Metalle aus der Gruppe gewählt sind, die mit Quecksilber Amalgame bilden. Es wird beispielsweise ein Edelmetalloxid, z.B. Silberoxid verwendet oder ein Mischoxid von zwei Edelmetallen oder von einem Edelmetall und einem weiteren Metall, z.B. Silber/Kupfer-Oxid. In einer bevorzugten Ausfüh-rungsform besteht die Beschichtung aus einem Silber/- Kupfer-Oxid mit einem SilbeπKupfer- Verhältnis von 1:5 bis 1:10.The coating of the channel walls consists of a metal oxide or mixed metal oxide, the metals being selected from the group which form amalgams with mercury. For example, a noble metal oxide, e.g. Silver oxide is used or a mixed oxide of two noble metals or one noble metal and another metal, e.g. Silver / copper oxide. In a preferred embodiment, the coating consists of a silver / copper oxide with a silver / copper ratio of 1: 5 to 1:10.
Wenn die Füllkörper 2 aus Metallblechen oder Metallfolien gefertigt sind, beispielsweise aus Edelstahlfolien, ist es vorteilhaft, die MetaUoberflächen, die die Innenoberflächen der Kanäle bilden, vor der Beschichtung mit den genannten Oxiden zur Vergrösserung der Oberfläche zuerst mit Alumim'umoxid oder Titanoxid zu beschichten.If the packings 2 are made of metal sheets or metal foils, such as stainless steel sheets, it is advantageous that MetaUoberflächen that form the inner surfaces of the channels, prior to coating with the said oxides to increase the surface first 'oxide with Alumim or coat titanium oxide.
Die Beschichtung mit Kupfer/Silber-Oxid wird beispielsweise realisiert durch Vorbehandeln der zu beschichtenden Edelstahlfohen mit Oxalsäure, durch Benetzen der vorbehandelten Oberflächen mit einer Lösung der entsprechenden Metall-Oxalate (z.B. Kupfer- und Silberoxalat) und durch nachträgliches Anlassen der benetzten Oberflächen in einer Wasserstoffatmosphäre.Coating with copper / silver oxide is achieved, for example, by pretreating the stainless steel foils to be coated with oxalic acid, by wetting the pretreated surfaces with a solution of the corresponding metal oxalates (e.g. copper and silver oxalate) and by subsequently tempering the wetted surfaces in a hydrogen atmosphere .
Die resultierenden Schichten haben eine Dicke von ca. 5 bis 10 μm. The resulting layers have a thickness of approximately 5 to 10 μm.

Claims

P A T E N T A N S P R Ü C H E P A T E N T A N S P R Ü C H E
Verfahren zur Entfernung von Quecksilber aus Abgasen, insbesondere aus Verbrennungsabgasen, dadurch gekennzeichnet, dass die Abgase über mit einem Oxid mindestens eines Metalles, das mit Quecksilber ein Amalgam bildet, beschichtete Oberflächen geleitet werden, wobei das Quecksilber von dem Oxid absorbiert wird. 5A method for removing mercury from exhaust gases, in particular from combustion exhaust gases, characterized in that the exhaust gases are passed over surfaces coated with an oxide of at least one metal which forms an amalgam with mercury, the mercury being absorbed by the oxide. 5
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das mindestens eine Metall ein Edelmetall ist oder ein Edelmetall und ein unedles Metall. 102. The method according to claim 1, characterized in that the at least one metal is a noble metal or a noble metal and a base metal. 10
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die Abgase in einer homogenen und gradlinigen Strömung über die Oberflächen geleitet werden. 153. The method according to any one of claims 1 or 2, characterized in that the exhaust gases are passed over the surfaces in a homogeneous and rectilinear flow. 15
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Abgase zwischen aufeinanderfolgendem Überleiten über die Oberflächen verwirbelt werden. 204. The method according to any one of claims 1 to 3, characterized in that the exhaust gases are swirled between successive transfer over the surfaces. 20th
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Abgase mit einer Geschwindigkeit von ca. 2 bis 3 m/s über die Oberflächen geleitet werden, derart, dass jedes Gasteilchen 25 im Mittel etwa zwei Mal mit der Oberfläche kollidiert. 5. The method according to any one of claims 1 to 4, characterized in that the exhaust gases are passed over the surfaces at a speed of about 2 to 3 m / s, such that each gas particle 25 collides with the surface about twice on average .
Vorrichtung zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 5, gekennzeichnet durch ein Gehäuse (1) mit einem Gaseinlass (E) und einem Gasauslass (A) und durch mindestens einen im Gehäuse (1) angeordneten Füllkörper (2), durch den der Innenraum des Gehäuses (1) in eine Mehrzahl von sich in der Richtung von Gaseinlass (E) zu Gasauslass (A) erstreckenden Kanälen (3) aufgeteilt wird, wobei die Innenwände der Kanäle (3) mit einem Oxid mindestens eines Metalls beschichtet sind, welches Metall mit Quecksilber ein Amalgam bildet. Device for carrying out the method according to one of claims 1 to 5, characterized by a housing (1) with a gas inlet (E) and a gas outlet (A) and by at least one filler (2) arranged in the housing (1), through which the Interior of the housing (1) is divided into a plurality of channels (3) extending in the direction from gas inlet (E) to gas outlet (A), the inner walls of the channels (3) being coated with an oxide of at least one metal, which Metal with mercury forms an amalgam.
1010
Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, dass die Kanäle geradlinig verlaufen.Apparatus according to claim 6, characterized in that the channels run in a straight line.
1515
Vorrichtung nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass im Gehäuse (1) zwischen Gaseinlass (E) und Gasauslass (A) eine Mehrzahl von Füllkörpern (2) angeordnet ist und dass die Füllkörper (2) voneinander beabstandet sind.Apparatus according to claim 6 or 7, characterized in that a plurality of fillers (2) is arranged in the housing (1) between the gas inlet (E) and gas outlet (A) and that the fillers (2) are spaced apart.
2020th
9. Vorrichtung nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass das Oxid ein Mischoxid von Kupfer und Silber ist.9. Device according to one of claims 6 to 8, characterized in that the oxide is a mixed oxide of copper and silver.
2525
10. Vorrichtung nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, dass die Oxidbeschichtung eine Dicke von ca. 5 bis 10 μm aufweist.10. Device according to one of claims 6 to 9, characterized in that the oxide coating has a thickness of about 5 to 10 microns.
3030
11. Vorrichtung nach einem der Ansprüche 6 bis 10, dadurch gekennzeichnet, dass der mindestens eine Füllkörper (2) ein extrudierter Keramikkörper ist oder aus strukturierten Metallblechen oder Metall- folien gefertigt ist.11. The device according to one of claims 6 to 10, characterized in that the at least one filler (2) is an extruded Is ceramic body or is made of structured metal sheets or metal foils.
12. Vorrichtung nach einem der Ansprüche 6 bis 11, dadurch gekennzeichnet, dass die Innenoberflächen der Kanäle (3) zur Oberflächen- vergrösserung unter der Beschichtung mit dem Oxid des mindestens einen mit Quecksilber ein Amalgam bildenden Metalls mit Alumi- niumoxid oder Titanoxid beschichtet sind.12. Device according to one of claims 6 to 11, characterized in that the inner surfaces of the channels (3) for increasing the surface area under the coating with the oxide of the at least one metal with mercury forming an amalgam are coated with aluminum oxide or titanium oxide.
1010
13. Vorrichtung nach einem der Ansprüche 6 bis 12, dadurch gekennzeichnet, dass die Kanäle (3) einen Querschnitt im Bereiche von 20 bis 30 mm2 und pro Füllkörper eine Länge im Bereiche von 0,3 m aufweisen. 1513. Device according to one of claims 6 to 12, characterized in that the channels (3) have a cross section in the range of 20 to 30 mm 2 and per filler body a length in the range of 0.3 m. 15
14. Verwendung eines Verfahrens nach einem der Ansprüche 1 bis 5 oder einer Vorrichtung nach einem der Ansprüche 6 bis 13 zur Entfernung von Quecksilber aus Abgasen von Verbrennungsanlagen, 20 insbesondere von Kehrichtverbrennungsanlagen, Klinikmüll- Verbrennungsanlagen, Altholz- Verbrennungsanlagen oder Krematorien, aus Abgasen von Sprengstoffbeseitigungsanlagen oder aus Produktions- ablüften.14. Use of a method according to one of claims 1 to 5 or a device according to one of claims 6 to 13 for removing mercury from exhaust gases from incineration plants, 20 in particular waste incineration plants, hospital waste incineration plants, waste wood incineration plants or crematoriums, from exhaust gases from explosive disposal plants or from production ventilation.
25 25
PCT/CH2000/000211 1999-04-15 2000-04-12 Method and device for exhaust gas cleaning WO2000062906A1 (en)

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Application Number Priority Date Filing Date Title
AU35486/00A AU3548600A (en) 1999-04-15 2000-04-12 Method and device for exhaust gas cleaning

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CH692/99 1999-04-15
CH69299 1999-04-15

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WO2000062906A1 true WO2000062906A1 (en) 2000-10-26

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Cited By (12)

* Cited by examiner, † Cited by third party
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US8876958B2 (en) 2011-12-15 2014-11-04 Clariant Corporation Composition and process for mercury removal
US20160023160A1 (en) * 2014-07-25 2016-01-28 Chemical and Metal Technologies LLC Emissions contaminant capture and collection device and method of use
US9381492B2 (en) 2011-12-15 2016-07-05 Clariant Corporation Composition and process for mercury removal
US9962650B2 (en) * 2014-07-25 2018-05-08 Chemical and Metal Technologies LLC Emissions contaminant capture and collection system utilizing an integrated fluidized bed apparatus and method of use
US9968884B2 (en) * 2014-07-25 2018-05-15 Chemical and Metal Technologies LLC Reconfigurable segmental contaminated emissions capture and collection system utilizing a fluidized bed apparatus with a method for tilting and/or agitation
US10035094B2 (en) * 2014-07-25 2018-07-31 Chemical and Metal Technologies LLC Broad-spectrum matrix for contaminated emissions sorbent compounds and method of use
CN108926980A (en) * 2017-05-26 2018-12-04 化学和金属技术有限责任公司 Use the capture of the emission pollutant of comprehensive fluidized bed plant and collection system and its application method
US10500569B2 (en) 2014-07-25 2019-12-10 Chemical and Metal Technologies LLC Emissions control system including capability to clean and/or rejuvenate CZTS sorbents, CZTS-alloy sorbents, and/or CZTS-mixture sorbents, and method of use
US10500539B2 (en) 2014-07-25 2019-12-10 Chemical and Metal Technologies LLC Emissions control system with CZTS sorbents, CZTS-based alloy sorbents, and/or carbon-based sorbents and method of use
US10500563B2 (en) 2014-07-25 2019-12-10 Chemical and Metal Technologies LLC Emissions control system including capability to clean and/or rejuvenate carbon-based sorbents and method of use
US10730012B2 (en) 2014-07-25 2020-08-04 Chemical and Metal Technologies LLC Extraction of target materials using CZTS sorbent
US10888836B2 (en) 2014-07-25 2021-01-12 Chemical and Metal Technologies LLC Extraction of target materials using CZTS sorbent

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DE2948305A1 (en) * 1979-11-30 1981-06-04 Deutsche Kommunal-Anlagen Miete GmbH, 8000 München Removing mercury vapour from hot waste gases - by finely divided metal which forms amalgam
DE4117828A1 (en) * 1991-05-29 1992-12-03 Eberhard Dipl Ing Kruemmel Material recovery process from small-arms ammunition - involves bonding mercury in fuse exhaust gas by forming amalgam in a reactor
US5409522A (en) * 1994-04-20 1995-04-25 Ada Technologies, Inc. Mercury removal apparatus and method

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DE2948305A1 (en) * 1979-11-30 1981-06-04 Deutsche Kommunal-Anlagen Miete GmbH, 8000 München Removing mercury vapour from hot waste gases - by finely divided metal which forms amalgam
DE4117828A1 (en) * 1991-05-29 1992-12-03 Eberhard Dipl Ing Kruemmel Material recovery process from small-arms ammunition - involves bonding mercury in fuse exhaust gas by forming amalgam in a reactor
US5409522A (en) * 1994-04-20 1995-04-25 Ada Technologies, Inc. Mercury removal apparatus and method

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9381492B2 (en) 2011-12-15 2016-07-05 Clariant Corporation Composition and process for mercury removal
US8876958B2 (en) 2011-12-15 2014-11-04 Clariant Corporation Composition and process for mercury removal
US10035094B2 (en) * 2014-07-25 2018-07-31 Chemical and Metal Technologies LLC Broad-spectrum matrix for contaminated emissions sorbent compounds and method of use
US9675933B2 (en) * 2014-07-25 2017-06-13 Chemical And Metal Technologies, Llc Emissions contaminant capture and collection device and method of use
US9962650B2 (en) * 2014-07-25 2018-05-08 Chemical and Metal Technologies LLC Emissions contaminant capture and collection system utilizing an integrated fluidized bed apparatus and method of use
US9968884B2 (en) * 2014-07-25 2018-05-15 Chemical and Metal Technologies LLC Reconfigurable segmental contaminated emissions capture and collection system utilizing a fluidized bed apparatus with a method for tilting and/or agitation
US20160023160A1 (en) * 2014-07-25 2016-01-28 Chemical and Metal Technologies LLC Emissions contaminant capture and collection device and method of use
US10500569B2 (en) 2014-07-25 2019-12-10 Chemical and Metal Technologies LLC Emissions control system including capability to clean and/or rejuvenate CZTS sorbents, CZTS-alloy sorbents, and/or CZTS-mixture sorbents, and method of use
US10500539B2 (en) 2014-07-25 2019-12-10 Chemical and Metal Technologies LLC Emissions control system with CZTS sorbents, CZTS-based alloy sorbents, and/or carbon-based sorbents and method of use
US10500563B2 (en) 2014-07-25 2019-12-10 Chemical and Metal Technologies LLC Emissions control system including capability to clean and/or rejuvenate carbon-based sorbents and method of use
US10730012B2 (en) 2014-07-25 2020-08-04 Chemical and Metal Technologies LLC Extraction of target materials using CZTS sorbent
US10888836B2 (en) 2014-07-25 2021-01-12 Chemical and Metal Technologies LLC Extraction of target materials using CZTS sorbent
US10994257B1 (en) 2014-07-25 2021-05-04 Chemical And Metal Technologies, Llc Extraction of target materials using CZTS sorbent
US11534734B2 (en) 2014-07-25 2022-12-27 Chemical and Metal Technologies LLC CZTS sorbent
CN108926980A (en) * 2017-05-26 2018-12-04 化学和金属技术有限责任公司 Use the capture of the emission pollutant of comprehensive fluidized bed plant and collection system and its application method

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