DE19939382A1 - Removing metallic mercury from hot pyrolysis gases produced from waste materials comprises adding metal sulfides to gases, mixing and removing solid reaction products on fine dust filters - Google Patents

Removing metallic mercury from hot pyrolysis gases produced from waste materials comprises adding metal sulfides to gases, mixing and removing solid reaction products on fine dust filters

Info

Publication number
DE19939382A1
DE19939382A1 DE1999139382 DE19939382A DE19939382A1 DE 19939382 A1 DE19939382 A1 DE 19939382A1 DE 1999139382 DE1999139382 DE 1999139382 DE 19939382 A DE19939382 A DE 19939382A DE 19939382 A1 DE19939382 A1 DE 19939382A1
Authority
DE
Germany
Prior art keywords
sulfide
metal sulfides
mercury
metallic mercury
sulfur
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
DE1999139382
Other languages
German (de)
Inventor
Konrad Fichtel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ftu Forschung und Tech En GmbH
Original Assignee
Ftu Forschung und Tech En GmbH
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
Priority to DE1999136930 priority Critical patent/DE19936930A1/en
Priority claimed from DE1999136930 external-priority patent/DE19936930A1/en
Application filed by Ftu Forschung und Tech En GmbH filed Critical Ftu Forschung und Tech En GmbH
Priority to DE1999139382 priority patent/DE19939382A1/en
Publication of DE19939382A1 publication Critical patent/DE19939382A1/en
Ceased legal-status Critical Current

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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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/003—Arrangements of devices for treating smoke or fumes for supplying chemicals to fumes, e.g. using injection devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/20—Sulfur; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/60—Heavy metals; Compounds thereof

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

Removing metallic mercury from hot pyrolysis gases produced from waste materials comprises adding metal sulfides that react with the mercury forming mercury sulfide to the pyrolysis gases, mixing and removing the solid reaction products on fine dust filters.

Description

Die Erfindung betrifft ein Verfahren und eine Vorrichtung zur Abscheidung von me­ tallischem Quecksilber aus heißen Prolysegasen von Abfallstoffen.The invention relates to a method and an apparatus for separating me metallic mercury from hot waste gases from waste materials.

Nach der Lehre der Hauptanmeldung P 199 36 930.5 werden zur Abscheidung von metallischem Quecksilber dem Pyrolysegas Schwefel, Schwefel-abgebende Stoffe, mit Schwefel beaufschlagte Aktivkohlen oder Herdofenkokse oder Schwefel auf an­ organischen Trägern zugesetzt und die entstehenden festen Reaktionsprodukte an Feinstaubfiltern abgeschieden.According to the teaching of the main application P 199 36 930.5 for the separation of metallic mercury the pyrolysis gas sulfur, sulfur-releasing substances, activated carbon or hearth furnace coke or sulfur on added organic carriers and the resulting solid reaction products Fine dust filters separated.

Bei Zusatz von Schwefel in jeglicher Form in das heiße Pyrolysegas kann dieser anteilig auch mit Bestandteilen des Pyrolysegases reagieren. Damit entsteht ein Mehrverbrauch an Schwefel.If sulfur is added to the hot pyrolysis gas in any form, it can partly react with components of the pyrolysis gas. This creates a Increased consumption of sulfur.

In Weiterbildung des Gegenstandes der Hauptanmeldung wird deshalb erfindungs­ gemäß vorgeschlagen, anstelle Schwefel Metallsulfide einzusetzen.In further training of the subject of the main application is therefore fiction proposed to use metal sulfides instead of sulfur.

Es wurde gefunden, daß bei Verwendung von Metallsulfiden die Reaktionen mit den Inhaltsstoffen des Pyrolysegases unterbleiben.It has been found that when using metal sulfides the reactions with the ingredients of the pyrolysis gas.

Als Metallsulfide werden bevorzugt Kupfersulfid, CuS, Zinksulfid, ZnS, Bleisulfid, PbS, Eisen(II)-Sulfid, FeS, Eisen(III)-Sulfid, Fe2S3, Kupferkies Cu2SxFe2S3, und/oder Buntkupfererz, 3Cu2SxFe2S3, eingesetzt. Preferred metal sulfides are copper sulfide, CuS, zinc sulfide, ZnS, lead sulfide, PbS, iron (II) sulfide, FeS, iron (III) sulfide, Fe2S3, copper gravel Cu2SxFe2S3, and / or colored copper ore, 3Cu2SxFe2S3.  

Die festen Metallsulfide werden als Pulver eingesetzt. Geeignet sind Korngrößen von 1 bis 200 µm, vorzugsweise von 1 bis 100 µm, insbesondere < 50 µm. Es kön­ nen jedoch auch Granulate verwendet werden oder Kombinationen von Metallsulfi­ den mit anorganischen Trägern, zu denen in diesem Falle auch die Aktivkohlen und Herdofenkokse gerechnet werden.The solid metal sulfides are used as powders. Grain sizes are suitable from 1 to 200 µm, preferably from 1 to 100 µm, in particular <50 µm. It can However, granules or combinations of metal sulfi can also be used with inorganic carriers, to which in this case also the activated carbons and Hearth furnace coke can be expected.

Entsprechend der Hauptanmeldung werden in einer vorteilhaften Ausführung der Erfindung Gemische aus Metallsulfiden und basischen Stoffen verwendet. Zu die­ sen zählen Calciumhydroxid, Branntkalk, Calciumcarbonat, Soda, Natriumhydro­ gencarbonat, Dolomit und/oder Natriumhydroxid. Diese Gemische sind bevorzugt Pulvergemische. Es lassen sich jedoch auch Suspensionen der basischen Stoffe und der Metallsulfide verwenden, insbesondere im Falle von Calciumhydroxid und Natriumhydroxid.According to the main application, the Invention mixtures of metal sulfides and basic substances used. To the Sen count calcium hydroxide, quicklime, calcium carbonate, soda, sodium hydro gene carbonate, dolomite and / or sodium hydroxide. These mixtures are preferred Powder mixtures. However, suspensions of the basic substances can also be used and the metal sulfides, especially in the case of calcium hydroxide and Sodium hydroxide.

Die Metallsulfide können in einem weiten Temperaturbereich eingesetzt werden. Entscheidend ist, daß der Taupunkt des Pyrolysegases nicht unterschritten wird. Geeignete Temperaturbereiche reichen von 200 bis 550°C, vorzugsweise von 350 bis 550°C. Ein besonders bevorzugter Bereich reicht von 450 bis 550°C, dem Tem­ peraturbereich des aus der Pyrolysevorrichtung kommenden Gases.The metal sulfides can be used in a wide temperature range. It is crucial that the dew point of the pyrolysis gas is not fallen below. Suitable temperature ranges are from 200 to 550 ° C, preferably from 350 up to 550 ° C. A particularly preferred range is from 450 to 550 ° C, the tem temperature range of the gas coming from the pyrolysis device.

Zu den Metallsulfid-Mengen ist festzustellen, daß sich diese nach der gewünschten Abscheidung von Quecksilber richten. Mehrfachstöchiometrische Mengen können bei den benötigten absolut geringen Mengen ohne Probleme eingesetzt werden.Regarding the amounts of metal sulfide, it should be noted that these vary according to the desired Straighten mercury separation. Multiple stoichiometric amounts can can be used with the absolutely small quantities required without any problems.

Im Rahmen der Erfindung liegt es auch die Metallsulfide in Kombination mit den in der Hauptanmmeldung aufgeführten Stoffe einzusetzen. Dies betrifft Gemische mit Schwefel, Schwefel auf anorganischen Trägern, Schwefel-abgebenden Substan­ zen, mit Schwefel dotierte Aktivkohlen, Herdofenkokse, Zeolithe, Bentonite, Trasse, Ziegelmehl und/oder Aluminiumoxide.In the context of the invention, it is also the metal sulfides in combination with the in substances listed in the main application. This affects mixtures with Sulfur, sulfur on inorganic supports, sulfur-releasing substance zen, sulfur-doped activated carbon, hearth furnace coke, zeolite, bentonite, route, Brick flour and / or aluminum oxides.

Mit den Metallsulfiden kann metallisches Quecksilber einfach und mit hohen Ab­ scheidegraden aus Pyrolysegasen abgeschieden werden.With the metal sulfides, metallic mercury can be easily and with high ab degrees of separation can be separated from pyrolysis gases.

Claims (7)

1. Verfahren zur Abscheidung von metallischem Quecksilber aus heißen Pyrolyse­ gasen von Abfallstoffen, dadurch gekennzeichnet, daß dem aus der Pyrolysevor­ richtung kommenden Pyrolysegas Metallsulfide, die mit metallischem Quecksilber unter Bildung von Quecksilbersulfid reagieren, zugesetzt, mit diesem vermischt und die festen Reaktionsprodukte des Quecksilbers an Feinstaubfiltern abgeschie­ den werden.1. A process for the deposition of metallic mercury from hot pyrolysis gases from waste materials, characterized in that the pyrolysis gas coming from the pyrolysis device metal sulfides, which react with metallic mercury to form mercury sulfide, added, mixed with this and the solid reaction products of the mercury Fine dust filters are separated. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Metallsulfide Kupfersulfid, CuS, Calciumsulfid, CaS, Zinksulfid, ZnS, Bleisulfid, PbS, Eisen(II)- Sulfid, FeS, Eisen(III)-Sulfid, Fe2S3, Kupferkies, Cu2SxFe2S3 und/oder Buntkupfererz, 3Cu2SxFe2S3, eingesetzt werden.2. The method according to claim 1, characterized in that as metal sulfides Copper sulfide, CuS, calcium sulfide, CaS, zinc sulfide, ZnS, lead sulfide, PbS, iron (II) - Sulfide, FeS, iron (III) sulfide, Fe2S3, copper gravel, Cu2SxFe2S3 and / or Colored copper ore, 3Cu2SxFe2S3, can be used. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Metallsulfide in feinpulvriger Form mit einer Korngröße von 1 bis 200 µm, vorzugsweise 1 bis 100 µm, insbesondere <50 µm eingesetzt, werden.3. The method according to claim 2, characterized in that the metal sulfides in finely powdered form with a grain size of 1 to 200 microns, preferably 1 to 100 µm, in particular <50 µm, are used. 4. Verfahren nach den vorhergehenden Ansprüchen, dadurch gekennzeichnet, daß zusätzlich basische Stoffe, wie Calciumhydroxid, Branntkalk, Calciumcarbonat, Soda, Natriumhydrogencarbonat, Dolomit und/oder Natriumhyroxid in das Pyrolysegas eingebracht werden.4. The method according to the preceding claims, characterized in that additionally basic substances such as calcium hydroxide, quicklime, calcium carbonate, Soda, sodium hydrogen carbonate, dolomite and / or sodium hydroxide in it Pyrolysis gas are introduced. 5. Verfahren nach den vorhergehenden Ansprüchen, dadurch gekennzeichnet, daß die Abscheidung des metallischen Quecksilbers im Temperaturbereich oberhalb des Taupunktes des Pyrolysegases bis 600°C durchgeführt wird. 5. The method according to the preceding claims, characterized in that the deposition of metallic mercury in the temperature range above the dew point of the pyrolysis gas is carried out up to 600 ° C.   6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Abscheidung des metallischen Quecksilbers im Temperaturbereich von 200 bis 550°C, vorzugsweise 350 bis 550°C, besonders bevorzugt von 450 bis 550°C, erfolgt.6. The method according to claim 5, characterized in that the deposition of the metallic mercury in the temperature range of 200 to 550 ° C, preferably 350 to 550 ° C, particularly preferably from 450 to 550 ° C, takes place. 7. Verfahren nach den vorhergehenden Ansprüchen, dadurch gekennzeichnet, daß zusätzlich zu den Metallsulfiden noch Schwefel, Kombinationen von Schwefel mit anorganischen Trägern, Schwefel-abgebende Substanzen, mit Schwefel dotierte Aktivkohlen, Herdofenkokse, Zeolithe, Bentonite, Trasse, Ziegelmehl und/oder Aluminiumoxide eingesetzt werden.7. The method according to the preceding claims, characterized in that in addition to the metal sulfides, sulfur, combinations of sulfur with inorganic carriers, sulfur-emitting substances, sulfur-doped Activated carbon, hearth furnace coke, zeolite, bentonite, route, brick powder and / or Aluminum oxides are used.
DE1999139382 1999-08-05 1999-08-19 Removing metallic mercury from hot pyrolysis gases produced from waste materials comprises adding metal sulfides to gases, mixing and removing solid reaction products on fine dust filters Ceased DE19939382A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE1999136930 DE19936930A1 (en) 1999-08-19 1999-08-05 Mercury removed from incinerated waste by combination with sulfur and filtration above dew point temperature of pyrolysis gases
DE1999139382 DE19939382A1 (en) 1999-08-05 1999-08-19 Removing metallic mercury from hot pyrolysis gases produced from waste materials comprises adding metal sulfides to gases, mixing and removing solid reaction products on fine dust filters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999136930 DE19936930A1 (en) 1999-08-19 1999-08-05 Mercury removed from incinerated waste by combination with sulfur and filtration above dew point temperature of pyrolysis gases
DE1999139382 DE19939382A1 (en) 1999-08-05 1999-08-19 Removing metallic mercury from hot pyrolysis gases produced from waste materials comprises adding metal sulfides to gases, mixing and removing solid reaction products on fine dust filters

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005107927A2 (en) 2004-04-29 2005-11-17 Solucorp Industries, Ltd. Air pollution control
WO2010002444A2 (en) * 2008-07-03 2010-01-07 Corning Incorporated Sorbent comprising activated carbon particles, sulfur and metal catalyst
CN106268625A (en) * 2016-09-30 2017-01-04 南京信息工程大学 Oxalic acid modification is given up brick, composite based on this useless brick and the method by its adsorbed water body heavy metal
CN106311280A (en) * 2016-08-31 2017-01-11 西安向阳航天材料股份有限公司 Copper sulfide containing mercury removal agent and preparation method thereof
CN115400725A (en) * 2022-08-18 2022-11-29 中南大学 Porous clay-based modified biochar composite material and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4764219A (en) * 1986-10-27 1988-08-16 Mobil Oil Corporation Clean up and passivation of mercury in gas liquefaction plants
US5110480A (en) * 1990-07-05 1992-05-05 Mobil Oil Corporation On-line rejuvenation of spent absorbents
US5190908A (en) * 1991-06-24 1993-03-02 Mobil Oil Corporation Racked bed for removal of residual mercury from gaseous hydrocarbons
US5350728A (en) * 1990-10-30 1994-09-27 Institut Francais Du Petrole And Europeene De Retraitment De Catalyseurs (Eurecat) Method of preparing a solid mass for mercury recovery
WO1994022563A1 (en) * 1993-04-06 1994-10-13 Shell Oil Company Volatile metals capture from gazeous streams
EP0496563B1 (en) * 1991-01-22 1996-08-28 Mobil Oil Corporation Simultaneous removal of residual impurities and moisture from a gas
DE19745191A1 (en) * 1997-10-13 1999-04-15 Ftu Gmbh Forschung Und Tech En Material for purifying gas to remove mercury and other pollutants

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4764219A (en) * 1986-10-27 1988-08-16 Mobil Oil Corporation Clean up and passivation of mercury in gas liquefaction plants
US5110480A (en) * 1990-07-05 1992-05-05 Mobil Oil Corporation On-line rejuvenation of spent absorbents
US5350728A (en) * 1990-10-30 1994-09-27 Institut Francais Du Petrole And Europeene De Retraitment De Catalyseurs (Eurecat) Method of preparing a solid mass for mercury recovery
EP0496563B1 (en) * 1991-01-22 1996-08-28 Mobil Oil Corporation Simultaneous removal of residual impurities and moisture from a gas
US5190908A (en) * 1991-06-24 1993-03-02 Mobil Oil Corporation Racked bed for removal of residual mercury from gaseous hydrocarbons
WO1994022563A1 (en) * 1993-04-06 1994-10-13 Shell Oil Company Volatile metals capture from gazeous streams
DE19745191A1 (en) * 1997-10-13 1999-04-15 Ftu Gmbh Forschung Und Tech En Material for purifying gas to remove mercury and other pollutants

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Derwent Abstracts: Ref. 1188W/07 zu JP 75001-477 *
Ref. 87-268022/38 zu JP 62186-925-A *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005107927A2 (en) 2004-04-29 2005-11-17 Solucorp Industries, Ltd. Air pollution control
EP1755771A2 (en) * 2004-04-29 2007-02-28 Solucorp Industries Ltd. Air pollution control
EP1755771A4 (en) * 2004-04-29 2007-12-26 Solucorp Ind Ltd Air pollution control
WO2010002444A2 (en) * 2008-07-03 2010-01-07 Corning Incorporated Sorbent comprising activated carbon particles, sulfur and metal catalyst
WO2010002444A3 (en) * 2008-07-03 2010-09-02 Corning Incorporated Sorbent comprising activated carbon particles, sulfur and metal catalyst
US8691722B2 (en) 2008-07-03 2014-04-08 Corning Incorporated Sorbent comprising activated carbon particles, sulfur and metal catalyst
CN106311280A (en) * 2016-08-31 2017-01-11 西安向阳航天材料股份有限公司 Copper sulfide containing mercury removal agent and preparation method thereof
CN106268625A (en) * 2016-09-30 2017-01-04 南京信息工程大学 Oxalic acid modification is given up brick, composite based on this useless brick and the method by its adsorbed water body heavy metal
CN106268625B (en) * 2016-09-30 2018-09-25 南京信息工程大学 The useless brick of oxalic acid modification, the composite material for the brick that given up based on this and the method with its adsorbed water body heavy metal
CN115400725A (en) * 2022-08-18 2022-11-29 中南大学 Porous clay-based modified biochar composite material and preparation method and application thereof

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