EP0377010A1 - Agent et procede pour purifier des gaz et des gaz d'echappement, et procede pour produire ledit agent - Google Patents

Agent et procede pour purifier des gaz et des gaz d'echappement, et procede pour produire ledit agent

Info

Publication number
EP0377010A1
EP0377010A1 EP19890906076 EP89906076A EP0377010A1 EP 0377010 A1 EP0377010 A1 EP 0377010A1 EP 19890906076 EP19890906076 EP 19890906076 EP 89906076 A EP89906076 A EP 89906076A EP 0377010 A1 EP0377010 A1 EP 0377010A1
Authority
EP
European Patent Office
Prior art keywords
substances
active substances
gases
heavy metals
calcium hydroxide
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
EP19890906076
Other languages
German (de)
English (en)
Inventor
Hermann Dr. Sucherwirth
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 GmbH
Original Assignee
FTU 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25868128&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0377010(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by FTU GmbH filed Critical FTU GmbH
Publication of EP0377010A1 publication Critical patent/EP0377010A1/fr
Ceased legal-status Critical Current

Links

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
    • 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
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/68—Halogens or halogen compounds
    • B01D53/70—Organic halogen compounds
    • 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
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/02—Lime
    • C04B2/04—Slaking
    • C04B2/06—Slaking with addition of substances, e.g. hydrophobic agents ; Slaking in the presence of other compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon

Definitions

  • the invention relates to an agent and a method for cleaning gases and exhaust gases and a method for the production of these agents.
  • the pollutants of importance include hydrogen chloride, hydrogen fluoride, sulfur dioxide, nitrogen oxides, carbon monoxide, heavy metals in volatile form, dioxins, furans, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons and the like, ie ecotoxic pollutants.
  • Elemental mercury is one of the substances that cause problems owing to their high volatility.
  • the polychlorinated dibenzodioxins and dibenzofurans which are considered harmful even in the smallest concentration, can be found in almost all gases according to conventional cleaning systems.
  • Activated carbon or activated coke is already used to remove the residual contents of acidic pollutants, chlorinated hydrocarbons, polycondensed aromatic hydrocarbons, volatile heavy metals and also NO with NH3 from exhaust gas streams.
  • the usual way of working is to pass the pre-cleaned exhaust gas over activated carbon fixed bed reactors or moving bed reactors.
  • the operating temperature is 80-150 degrees C.
  • This method of operation is effective when an exhaust gas is used which contains only low levels of sulfur dioxide, HC1 and dust, which requires efficient, upstream exhaust gas cleaning.
  • a further disadvantage is that the coal can self-ignite in the activated carbon reactors. This is the case in particular in the event of operational downtimes.
  • Activated carbon accumulations can occur in the reaction product, which give rise to smoldering fires in activated carbon nests in the intermediate storage containers. Furthermore, the uniform distribution of the activated carbon in the exhaust gas stream causes problems during direct injection.
  • the uniform suspension of activated carbon in the calcium hydroxide suspension is also not easy and gives rise to fluctuating separation rates, so that compliance with the limit values is problematic.
  • the invention further provides a method for producing dry powders based on calcium hydroxide for gas and exhaust gas purification according to independent claim 9. Preferred developments of these methods are described in the dependent 10-15 patent claims.
  • the object is achieved in two stages in that, in a first stage, reactive calcium hydroxides are prepared which contain surface-active substances which, in a second stage, are used to act on the pollutants of exhaust gases in a dry process , and be separated again from the exhaust gas stream.
  • the process according to the invention for producing reactive calcium hydroxide for gas and exhaust gas purification is characterized in that surface-active substances are added to the quicklime before the quicklime is extinguished, to the extinguishing water during the extinguishing and to the calcium hydroxide after the extinguishing.
  • silica gel, diatomaceous earth, activated aluminum oxide, activated carbon and or hearth furnace lignite coke in powder form are used as surface-active substances.
  • the average active surface for activated carbon is around 600 m2 / g.
  • the pollutants are deposited on these active surfaces, in particular mercury, dioxins, PCßs, but also to a certain extent S02, HC1 and NOx. These substances remain there or ⁇ can be converted into other substances.
  • the surface-active substances are used as powders.
  • the surface-active substances have a grain size, determined as a sieve passage, of ⁇ 200ug. A grain size which corresponds to that of calcium hydroxide powder is preferred.
  • the process according to the invention can also advantageously be carried out by subjecting the powdery surface-active substances to catalysts for oxidation, reduction and / or decomposition reactions before they are used for the treatment of gases and exhaust gases.
  • the application takes place in such a way that the corresponding heavy metals are applied to the surface-active substances as water-soluble salts or dissolved in organic solvents, and the surface-active substances are then subjected to drying.
  • catalysts for a wide variety of reactions on the surface-active substances are also advantageously be carried out by subjecting the powdery surface-active substances to catalysts for oxidation, reduction and / or decomposition reactions before they are used for the treatment of gases and exhaust gases.
  • alcoholic solutions can also be used.
  • Water-soluble chlorides and nitrates are predominantly used as salts.
  • the heavy metal binding substances are water-soluble sulfides, e.g. Sodium sulfide and mercaptans, or trimercapto-s-triazine for use.
  • the combination of the activated carbon provided with heavy metals with calcium hydroxide has a multiple function.
  • the presence of the inorganic substance reduces the risk of burning the active carbons loaded with heavy metals. Effective inhibition occurs when calcium hydroxide as a fine powder together with the Activated carbons are present.
  • the risk of ignition can be suppressed particularly strongly if the activated carbons are mixed together with quicklime and then subjected to an extinguishing reaction, so that activated carbon and calcium hydroxide are present in very fine distribution, in some cases. Calcium hydroxide is deposited in the pores of the activated carbon.
  • a further embodiment of the production of the reactive calcium hydroxides consists in mixing the surface-active substances with quicklime and adding the pollutant-binding and / or catalytically active substances to the extinguishing water.
  • calcium hydroxide and surface-active substances are mixed, the latter possibly. are acted upon by catalytically active and / or heavy metal-binding substances.
  • a special embodiment of the production of reactive calcium hydroxides according to the invention consists in using surface-active substances which have a catalytic effect with heavy metals which have an effect on oxidation or reduction processes, and with substances with a basic effect, such as sodium hydrogen carbonate, sodium carbonate, sodium hydroxide and the like. are acted upon. With this combination of heavy metals and basic compounds on surface-active substances, oxidation and reduction processes can be controlled via potential changes.
  • the acids also act on the heavy metals with regard to the form of the compound and redox potential.
  • the calcium hydroxides containing surface-active substances produced according to the invention are used in the process according to the invention for cleaning exhaust gases.
  • the process according to the invention for the purification of gases and exhaust gases from acidic pollutants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, hydrocyanic acid and the like, nitrogen oxides, hydrocarbons, chlorinated hydrocarbons, organic compounds and volatile heavy metals, e.g.
  • Mercury, arsenic, antimony, cadmium and thalium, using surface-active substances is characterized in that finely powdered, dry calcium hydroxide is added to the gas or exhaust gas stream, which contains surface-active substances such as activated carbon, lignite Oven coke, silica gel, silica and / or active aluminum oxide contains, added and mixed with the exhaust gas stream in a reactor and the calcium hydroxide powder with the bound pollutants without lowering the reaction temperature on dust separating devices, in particular on fabric filters or electrostatic precipitators from which gas flow is separated.
  • surface-active substances such as activated carbon, lignite Oven coke, silica gel, silica and / or active aluminum oxide
  • a drop in temperature e.g. from 200 to 120 degrees C, as is practiced, is not necessary in order to remove dioxins, PAHs and mercury as far as possible.
  • Calcium hydroxides which have been produced from quicklime, mixed with surface-active substances, are particularly resistant to separation.
  • Pneumatic devices are preferably used to inject the modified calcium hydroxides.
  • the used Ca (0H) 2 is preferably separated on fabric filters. E-filters are also suitable.
  • activated carbon / activated coke also acts as a catalyst for reducing NOx with NH3 to N2.
  • This embodiment of the invention is suitable when no or little acidic pollutants are present in the exhaust gas, that is to say that the expensive basic Ca (0H) 2 can be dispensed with.
  • the treatment of the exhaust gas with the surface-active substances takes place in the temperature range of 20-1200 degrees C, preferably in the range of 80-250 degrees C, in particular in the range of 170-240 degrees C, more preferably in the temperature range from 180-220 degrees C.
  • the water content of the exhaust gas is decisive for the choice of temperature.
  • the lowest temperature limit should be 30 to 40 degrees C above the dew point.
  • the temperature should not drop below 130 to 140 degrees C, since otherwise encrustations occur on the tissue filter.
  • An advantageous form of the process according to the invention is that in a multi-stage process the gases and exhaust gases are first subjected to dry or wet cleaning and then for the residual separation of the inorganic and organic pollutants the gases and exhaust gases with substances which contain surface-active substances. if necessary are treated with heavy metals, are treated, in order to reduce nitrogen oxides in the gas stream prior to treatment with the surface-active substances, ammonia or suitable nitrogen-containing compounds, e.g. Urea are added.
  • the heavy metals to the surface-active substances ha ⁇ the function ben the oxidation of S02 to S03, C0 to C02, NO to N02 and Sieren hydrocarbons to C02 and H20 to catalytically ".
  • the oxidation of sulfur dioxide to sulfur trioxide has the advantage that the more volatile sulfur trioxide is formed from the volatile sulfur dioxide, which is preferably deposited on the surface-active substances.
  • the surface-active substances are used together with basic substances, be it lime or calcium hydroxide, then immediate implementation with these basic substances is also possible.
  • Particularly favorable catalysts for this are manganese, vanadium, iron and platinum.
  • a further possibility is to convert the carbon monoxide which is always present in the exhaust gases into harmless carbon dioxide using the catalysts and the oxygen present.
  • the chlorinated or sulfur-containing hydrocarbons can also be oxidized to the basic compounds C02, H20, HC1 and / or S02 in residual contents and thus removed as ecotoxic pollutants.
  • Chromium, vanadium, iron, palladium, copper and manganese are particularly suitable for the oxidation of organic substances.
  • nitrogen monoxide which can be converted to nitrogen dioxide with the action of catalysts, in particular chromium, titanium, iron and manganese.
  • catalysts in particular chromium, titanium, iron and manganese.
  • This is water-soluble and can be washed out of the exhaust gas stream.
  • it can be converted into non-volatile salts immediately in the presence of basic substances.
  • the reduction of nitrogen oxide with ammonia or nitrogen-containing compounds, e.g. Urea is favored by the heavy metal catalysts.
  • the effect of the oxidation catalysts for sulfur dioxide and also for nitrogen oxide can be increased if the surface-active substances together with the heavy metals also have basic-acting substances, for example sodium hydroxide, sodium carbonate, sodium bicarbonate, etc. be worn. As the oxidation takes place in the direct vicinity of the basic substances, the higher oxides of sulfur and nitrogen can be integrated immediately.
  • basic-acting substances for example sodium hydroxide, sodium carbonate, sodium bicarbonate, etc.
  • This method of operation is particularly important when the method according to the invention is used for the residual removal of acidic pollutants.
  • the surface-active substances can preferably be used for residual cleaning. This applies in particular to organic substances and also to the residual levels of hydrogen chloride and sulfur dioxide.
  • the process is particularly important for the deposition of nitrogen oxides.
  • the conventional cleaning methods do capture hydrogen fluoride, hydrogen chloride and sulfur dioxide to a sufficient extent, but are only able to separate the nitrogen oxide to a small extent.
  • the subsequent cleaning with the aid of surface-active substances to which catalysts have been applied means that nitrogen oxide can either be oxidized and then separated with basic substances, or reduced to nitrogen with ammonia.
  • the use of the surface-active substances charged with heavy metals in combination with Ca (0H) 2 or inorganic dusts is of course not restricted to use in a post-cleaning stage, but also includes the initial use.
  • the method according to the invention is for the treatment of gases and exhaust gases from power plants, from waste incineration plants, from special waste incineration plants, from combustion plants, from plants for the production of glass and ceramics, from plants for remelting old aluminum and also for treating gases and exhaust gases from numerous production processes, e.g. . B. the smelting of ores, and other industrial processes, can be used.
  • HgC12 content 1.29 ⁇ g / l
  • Lignite hearth coke in combination with inert material is also suitable for mercury separation from exhaust gases.
  • A1203 is therefore suitable as a sorbent for the separation of mercury from exhaust gases.
  • the waste gas from a waste incineration plant was dry cleaned with Ca (0H) 2 at 200 degrees Celsius.
  • the content of which in the raw gas was 330 ⁇ g / m3
  • 25 kg of Ca (0H) 2 and 1.25 kg of lignite-hearth furnace coke dust were blown in per ton of waste, mixed in a reactor and separated on a fabric filter.
  • Ca (0H) 2 and coke dust had been mixed beforehand.

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

Abstract

Des tensioactifs tels que du charbon actif, du coke de lignite de four à sole, de l'oxyde d'aluminium activé et du gel de silice sont ajoutés, sous une forme finement divisée, à l'eau nécessaire à l'extinction de la chaux vive. Le Ca(OH)2 obtenu convient particulièrement pour éliminer le Hg des gaz et des gaz d'échappement. Des teneurs résiduelles en HCl, SO2 et NOx peuvent également être éliminées. Les tensioactifs peuvent aussi être mélangés à la chaux vive avant son extinction ou bien au Ca(OH)2. Les tensioactifs peuvent être chargés de métaux lourds catalytiquement actifs, par exemple du vanadium, ou bien de substances qui lient les métaux lourds, par exemple du sulfure de sodium. Les tensioactifs utilisés sont du charbon actif, du coke de lignite de four à sole, du gel de silice, de la diatomite et/ou de l'alumine activée.
EP19890906076 1988-05-16 1989-05-16 Agent et procede pour purifier des gaz et des gaz d'echappement, et procede pour produire ledit agent Ceased EP0377010A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3816595 1988-05-16
DE3816595 1988-05-16
DE3838987 1988-11-18
DE3838987 1988-11-18

Publications (1)

Publication Number Publication Date
EP0377010A1 true EP0377010A1 (fr) 1990-07-11

Family

ID=25868128

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890906076 Ceased EP0377010A1 (fr) 1988-05-16 1989-05-16 Agent et procede pour purifier des gaz et des gaz d'echappement, et procede pour produire ledit agent

Country Status (3)

Country Link
EP (1) EP0377010A1 (fr)
DE (1) DE3915934C2 (fr)
WO (1) WO1989011329A1 (fr)

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