WO2000041796A1 - Gas purifying agent, its method of production and its use - Google Patents

Gas purifying agent, its method of production and its use Download PDF

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Publication number
WO2000041796A1
WO2000041796A1 PCT/EP2000/000239 EP0000239W WO0041796A1 WO 2000041796 A1 WO2000041796 A1 WO 2000041796A1 EP 0000239 W EP0000239 W EP 0000239W WO 0041796 A1 WO0041796 A1 WO 0041796A1
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group
acid
representatives
agent
substances
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PCT/EP2000/000239
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German (de)
French (fr)
Inventor
Konrad Fichtel
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Ftu Gmbh Forschung Und Technische Entwicklung Im Umweltschutz
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Priority to EP00907473A priority Critical patent/EP1144091A1/en
Publication of WO2000041796A1 publication Critical patent/WO2000041796A1/en

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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • 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
    • B01D53/04—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 stationary adsorbents
    • 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
    • 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
    • B01D53/38—Removing components of undefined structure
    • B01D53/44—Organic components
    • 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
    • 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
    • B01D53/54—Nitrogen 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
    • B01D53/64—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
    • B01D53/68—Halogens or 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
    • B01D53/68—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts

Definitions

  • Agents process for making the agent and use of the agent for gas purification
  • the invention relates to an agent, a method for producing the agent and the use of the agent for gas cleaning.
  • thermal processes e.g. Smelter processes
  • coal firing waste incineration and numerous industrial processes produce exhaust gases that are mixed with volatile heavy metals, e.g. Cadmium, mercury, thallium, arsenic, antimony and lead are contaminated.
  • volatile heavy metals e.g. Cadmium, mercury, thallium, arsenic, antimony and lead are contaminated.
  • elemantare i.e. zero-valent heavy metals or salts, preferably chlorides and oxides.
  • organic pollutants e.g. Dioxins, furans, aromatics and the like.
  • the gases are usually cooled down and the pollutants are washed out wet. This is often not sufficient if the heavy metals are in elemental form. Mercury e.g. is often emitted as an element. It cannot then be separated from the gas using wet washing. In addition, there is the problem that volatile heavy metal salts are emitted as aerosols and / or fine dust that is difficult to separate even after wet washing. The dioxins, aromatics and halogenated hydrocarbons are also insufficiently separated.
  • Another method is to route exhaust gas flows through activated carbon filters. This leads to a decrease in the volatile content
  • Pollutants such as mercury
  • This process is associated with considerable costs because large amounts of highly active coal are used and there is always the risk of smoldering fires in the coal bed.
  • the abrasion that is always present also emits pollutant-containing fine dust, which is difficult to separate.
  • Another method is to apply sulfur to activated carbon and to conduct the gas stream over it.
  • the mercury separation and separation of organic pollutants is quite effective, but the problems of spontaneous combustion and the emission of abrasion remain.
  • the use of sulfided coal fails because of its exorbitant price.
  • the oxidizing agents used preferably hydrogen peroxide, react with all oxidizable substances, e.g. Sulfur dioxide. This means a considerable additional consumption of oxidizing agent.
  • hydrogen peroxide decomposes on the dust of the exhaust gas, e.g. Flying dust, calcium hydroxide, activated carbon and stove coke.
  • the nitrogen oxide content is currently reduced by reduction with ammonia over expensive catalysts. This process is expensive and requires its own part of the plant.
  • the object of the invention is to satisfy the needs listed above and to provide a suitable means.
  • an agent which consists of - Group A: porous, acid-resistant, inorganic substances;
  • Group B inorganic and / or organic acids which are absorbed in the porous, acid-resistant, inorganic substances;
  • - Group C surface-active substances
  • - Group D basic substances, where the representatives of groups A, B and C must always be present, whereas those of group D are used alternatively.
  • the invention is based on having found that the separation performance of the known surface-active substances is achieved by
  • Exposure to acids, which are absorbed in porous, acid-resistant, inorganic substances and during the The deposition process together with the surface-active substances can be improved.
  • Fired clays, diatomaceous earth, perlite, pumice stone, expanded clay, gas concrete, aluminum oxide and / or silica gel are suitable as representatives of group A in powdered or granular form. These substances are highly oxidized compounds which, due to their production, are both stable against acids and have a certain acid pore volume for the acids mentioned.
  • the acid pore volume is determined by adding fine powder, porous, acid-resistant, inorganic material to 1 g of the acid until a dry powder is obtained.
  • the dry mixture of brick powder consists of 75% by weight brick powder and 25% by weight sulfuric acid
  • the dry mixture of diatomaceous earth it consists of 52% by weight kieselguhr and 48% by weight sulfuric acid.
  • the acid-pore volume can be determined for all substances listed and also for all acids.
  • the inorganic or organic acids which are absorbed in the porous, acid-resistant, inorganic substances include sulfuric acid, hydrochloric acid, nitric acid, acetic acid and formic acid. Of the acids listed, sulfuric acid is preferred. Sulfuric acid acts both as an acid and as a strong oxidizing agent in the Exhaust gas cleaning temperatures. This means that O-valent mercury is oxidized to 1- or 2-valent mercury. The oxidation takes place either in the gas space or on the surface-active substances, on which sulfuric acid is also deposited. Not only are volatile heavy metals oxidized, but also organic pollutants, such as especially chlorinated dioxins and furans, chlorinated aromatic and aliphatic hydrocarbons, chlorinated biphenyls, aromatic hydrocarbons and other toxic organic compounds.
  • Nitric acid has a similar effect to that of sulfuric acid, which in addition to its acidic effect also has oxidizing properties.
  • Hydrochloric acid, acetic acid and formic acid are not oxidizing and therefore essentially increase the separation of volatile heavy metals, especially mercury, even in elemental form, surprisingly on the surface-active substances mentioned.
  • Activated carbons of the most varied production brown coal hearth coke (hereinafter referred to only as hearth coke or HOK), activated aluminum oxide and / or silica gel are suitable as surface-active substances. It is known that the activated carbons and also hearth furnace coke are particularly suitable for the separation of organic substances and volatile heavy metals. However, there is always a risk of the occurrence of these purely carbon-containing substances Smoldering. It is therefore appropriate to use aluminum oxide or silica gel in fire-critical situations.
  • the agent according to the invention forms a universal system for the excellent separation of volatile heavy metals and organic pollutants and also of nitrogen oxides, in particular nitrogen monoxide.
  • the external form of the product is either in powder form or as granules.
  • powdery form with a grain size ⁇ 100 ⁇ m, preferably ⁇ 50 ⁇ m, preferably ⁇ 10 // m, it serves as an adsorbent in the entrained flow process.
  • the grain size is between 1 and 10 mm, preferably between 2 and 5 mm.
  • the granularity of the individual components is appropriately coordinated so that no segregation can occur when a mixture is used. This applies in particular to the use of dust-like agents in which there is a possibility of segregation due to the turbulence caused in the exhaust gas.
  • the acids can be present in the porous inorganic substances in an aqueous solution of any concentration or, in the case of sulfuric acid, acetic acid and formic acid, in an anhydrous form.
  • sulfuric acid in particular, it is advisable to work with concentrated sulfuric acid, since the need for porous inorganic substances is low and the oxidizing effect of sulfuric acid is higher.
  • a preferred agent consists of porous brick powder and / or diatomaceous earth with absorbed sulfuric acid, nitric acid and / or hydrochloric acid and activated carbon and / or hearth furnace coke and calcium hydroxide and / or calcium carbonate.
  • the preferred agent can both separate the volatile heavy metals well and also significantly reduce the content of numerous organic pollutants and also nitrogen oxides.
  • the presence of calcium hydroxide and / or calcium carbonate also leads to a sufficient reduction in the content of hydrogen chloride and sulfur dioxide in the exhaust gas.
  • the amounts of the individual components can be varied within a wide range in the agent according to the invention.
  • the content of basic substances primarily calcium hydroxide, depends on the content of hydrogen chloride and sulfur dioxide.
  • the content is then preferably 45-98% by weight of basic substances.
  • the surface-active substances preferably have a content of 1 to 50% by weight, while group A with the absorbed acids preferably has a proportion of 1 to 5% by weight. With this proportion of porous, inorganic, acid-resistant substances, the amount of acid absorbed is sufficient to oxidize the volatile heavy metals, especially the 0-valent mercury and also the organic substances. In addition, the proportion of nitrogen oxides can be significantly reduced.
  • the agent consists of porous brick powder and / or diatomaceous earth with absorbed sulfuric acid, nitric acid and / or hydrochloric acid and activated carbon and / or hearth furnace coke.
  • the agent is used to purify exhaust gases that have already been pre-cleaned in a cleaning process, be it in the entrained flow process in a dry version or in the wet process. Since the majority of the acidic components, hydrogen chloride and sulfur dioxide, have already been removed, the presence of the basic substances can be dispensed with.
  • Another application is when the gases to be cleaned are acid-free.
  • the basic agents can be added in small amounts. The amount required to neutralize the amount of acids introduced is sufficient.
  • the composition consists of 1 to 10% by weight of a representative of group A with absorbed acids and 90 to 99% by weight of representatives of group C, that is to say the surface-active substances.
  • the agents according to the invention can be prepared by the method according to the invention in that the representatives of the listed components are mixed dry. This is expediently done by adding large amounts of representatives of group A, ie the porous, acid-resistant, inorganic substances, to the acids until a powder with the usual flow, flow and flight properties is obtained. This mixture of representatives of group A and group B is then mixed with the likewise powdery and dry representatives of group C and optionally also with D. There is then an easy-to-use powdery mixture that can be used for the entrained-flow process.
  • the agent according to the invention can also be present as granules.
  • the representatives of groups C and D are produced in a known manner into granules whose grain size is in the range from 1 to 10 mm, preferably 2 to 5 mm.
  • Granular material from group A which contains the acids, is now added to these granules. This mixture of granulated and granular material can then be used for exhaust gas cleaning in a fixed bed.
  • Is group D i.e. dispenses with the basic materials, then a mixture of granular surface-active substances and granular material from group A, which contains the acids, is prepared.
  • the agent according to claims 1 to 9 is used according to the invention to remove volatile heavy metals, in particular elemental heavy metals, chlorinated dioxins and furans, chlorinated aromatic and aliphatic hydrocarbons, chlorinated biphenyls, aromatic hydrocarbons, toxic organic compounds, hydrogen chloride and / or sulfur dioxide and nitrogen oxides from gases , in particular exhaust gases, used by breaking into the gas stream, treating harmful constituents of the gas with the agent at a temperature of 20 to 400 ° C., in particular 60 to 250 ° C., preferably 1 20 to 210 ° C., and the reaction products as well unreacted agent can be separated on fabric filters or electrostatic filters.
  • This method consists in that the pulverulent material is injected into the exhaust gas stream in a known manner, swirled in the latter and then the solids are applied to a fabric filter or an electrostatic filter.
  • the temperature must be so high that there is no condensation of water on the agent according to the invention. In general a temperature of 30 ° C above the dew point of the gas is selected.
  • the agent is preferably used in dry sorption, conditioned dry sorption and spray sorption. Depending on the structure of the cleaning process, the agent can be introduced into the gas stream at various points in the exhaust gas cleaning system. The addition is preferably carried out as a mixture of all substances.
  • Spray sorption must be carried out in such a way that the agent can only be added without the basic components of group D after the drying process has been carried out. That is, an agent is used from the representatives of group A, which contain the acids, and representatives of group C, the surface-active substances.
  • Example 1 comparative example
  • a mixture of 98% by weight Ca (OH) 2 and 2% by weight brick powder / sulfuric acid powder was prepared from calcium hydroxide (Ca (OH 2 ) and this brick powder / sulfuric acid mixture.
  • Adsorbent produced the following composition.

Abstract

The invention relates to an agent for purifying gases and exhaust gases, consisting of A) porous, acid-resistant, inorganic substances such as brick dust or kieselguhr; B) inorganic and/or organic acids which have been absorbed by the porous, acid-resistant, inorganic substances; C) surface-active substances; and possibly D) basic substances. The above agent is used to purify gases at temperatures of between 20 and 400 DEG C.

Description

Mittel, Verfahren zur Herstellung des Mittels und Verwendung des Mittels zur GasreinigungAgents, process for making the agent and use of the agent for gas purification
Beschreibungdescription
Die Erfindung betrifft ein Mittel, ein Verfahren zur Herstellung des Mittels und die Verwendung des Mittels zur Gasreinigung.The invention relates to an agent, a method for producing the agent and the use of the agent for gas cleaning.
Bei thermischen Prozessen, z.BN. Hüttenprozessen, Kohlefeuerungen, Abfallverbrennungen und zahlreichen industriellen Verfahren werden Abgase erzeugt, die mit flüchtigen Schwermetallen, z.B. Cadmium, Quecksilber, Thallium, Arsen, Antimon und Blei belastet sind. Es handelt sich dabei um elemantare, d.h. nullwertige Schwermetalle oder Salze, vorzugsweise Chloride und Oxide. Weiterhin enthalten sie noch in vielen Fällen organische Schadstoffe, z.B. Dioxine, Furane, Aromaten u.dgl.In thermal processes, e.g. Smelter processes, coal firing, waste incineration and numerous industrial processes produce exhaust gases that are mixed with volatile heavy metals, e.g. Cadmium, mercury, thallium, arsenic, antimony and lead are contaminated. These are elemantare, i.e. zero-valent heavy metals or salts, preferably chlorides and oxides. Furthermore, they still contain organic pollutants in many cases, e.g. Dioxins, furans, aromatics and the like.
Üblicherweise werden die Gase abgekühlt und die Schadstoffe nass ausgewaschen. Häufig ist dies nicht ausreichend, wenn die Schwermetalle in elementarer Form vorliegen. Quecksilber z.B. wird vielfach als Element emittiert. Es lässt sich dann auch über eine Nasswäsche nicht aus dem Gas abtrennen. Hinzu kommt noch das Problem, dass flüchtige Schwermetallsalze auch nach der Nasswäsche als Aerosole und/oder schwer abscheidbarer Feinstaub emittiert werden. Auch die Dioxine, Aromaten und Halogenkohlenwasserstoffe werden nur unzureichend abgeschieden.The gases are usually cooled down and the pollutants are washed out wet. This is often not sufficient if the heavy metals are in elemental form. Mercury e.g. is often emitted as an element. It cannot then be separated from the gas using wet washing. In addition, there is the problem that volatile heavy metal salts are emitted as aerosols and / or fine dust that is difficult to separate even after wet washing. The dioxins, aromatics and halogenated hydrocarbons are also insufficiently separated.
Eine andere Methode besteht darin, Abgasströme über Aktivkohlefilter zu leiten. Dies führt zu einer Verminderung des Gehaltes an flüchtigenAnother method is to route exhaust gas flows through activated carbon filters. This leads to a decrease in the volatile content
Schadstoffen, z.B. von Quecksilber, doch ist dieses Verfahren mit erheblichen Kosten belastet, da große Mengen hochaktiver Kohle eingesetzt werden müssen und immer die Gefahr der Schwelbrände im Kohlebett besteht. Über den stets vorhandenen Abrieb wird außerdem schadstoffhaltiger Feinstaub emittiert, der schwierig abzuscheiden ist.Pollutants, such as mercury, but this process is associated with considerable costs because large amounts of highly active coal are used and there is always the risk of smoldering fires in the coal bed. The abrasion that is always present also emits pollutant-containing fine dust, which is difficult to separate.
Ein weiteres Verfahren besteht darin, Schwefel auf Aktivkohle aufzubringen und den Gasstrom darüber zu leiten. Die Quecksilberabscheidung und die Abtrennung organischer Schadstoffe ist zwar recht wirksam, doch bleiben die Probleme der Selbstentzündung und der Emission von Abrieb bestehen. Hinzu kommt noch, dass der Einsatz von sulfidierter Kohle am exorbitanten Preis derselben scheitert.Another method is to apply sulfur to activated carbon and to conduct the gas stream over it. The mercury separation and separation of organic pollutants is quite effective, but the problems of spontaneous combustion and the emission of abrasion remain. In addition, the use of sulfided coal fails because of its exorbitant price.
Es hat deshalb nicht an weiteren Versuchen gefehlt, die Abscheidung von elementarem Quecksilber durch Oxidation zu ein- oder zweiwertigem Quecksilber zu verbessern.There has therefore been no lack of further attempts to improve the separation of elemental mercury by oxidation to monovalent or divalent mercury.
Die eingesetzten Oxidationsmittel, vorzugsweise Wasserstoffperoxid, reagieren jedoch mit allen oxidierbaren Stoffen, z.B. Schwefeldioxid. Dies bedeutet einen erheblichen Mehrverbrauch an Oxidationsmittel. Außerdem zersetzt sich Waserstoffperoxid an den Stäuben des Abgases, z.B. Flugstaub, Calciumhydroxid, Aktivkohle und Herdofenkoks.However, the oxidizing agents used, preferably hydrogen peroxide, react with all oxidizable substances, e.g. Sulfur dioxide. This means a considerable additional consumption of oxidizing agent. In addition, hydrogen peroxide decomposes on the dust of the exhaust gas, e.g. Flying dust, calcium hydroxide, activated carbon and stove coke.
Auch dies bedeutet einen erheblichen Mehrverbrauch an Oxidationsmittel.This also means a considerable increase in the consumption of oxidizing agents.
Es liegt demnach das Bedürfnis vor, aus den Gasströmen, vornehmlich von Abfallverbrennungsanlagen, flüchtige Schwermetalle, insbesondere Quecksilber, in ihren verschiedenen Verbindungsformen und auch als Elemente, gezielt, einfach und preiswert abzuscheiden, aber auch organische Schadstoffe, wie Dioxide und Furane zu erfassen und ebenfalls abzuscheiden. Weiterhin besteht die Aufgabe, ein einfaches und kostengünstiges Verfahren zur gemeinsamen Abscheidung von flüchtigen anorganischen und organischen Schadstoffen und sauren Bestandteilen aus Gasströmen zu entwickeln. Dabei muss die Verminderung des Schadstoffgehaltes im Abgasstrom so hoch sein, dass die bestehenden Grenzwerte, z.B. für Hg, Cd, Tl und Dioxine/Furene, sicher eingehalten werden können.Accordingly, there is a need to separate volatile heavy metals, in particular mercury, from the gas streams, primarily from waste incineration plants, in their various forms of connection and also as elements, in a targeted, simple and inexpensive manner, but also to record and also record organic pollutants such as dioxides and furans to separate. Furthermore, there is the task of developing a simple and inexpensive process for the joint separation of volatile inorganic and organic pollutants and acidic constituents from gas streams. The reduction of the The pollutant content in the exhaust gas flow must be so high that the existing limit values, e.g. for Hg, Cd, Tl and dioxins / furene, can be safely adhered to.
Außerdem besteht die Notwendigkeit, den Anteil der oberflächenaktiven Substanzen in den Sorbentien zu vermindern, da sie teuer sind.There is also a need to reduce the level of surfactants in the sorbents because they are expensive.
Weiterhin besteht das Bedürfnis, den Gehalt an Stickstoffoxiden so weit zu vermindern, dass die gesetzlichen Grenzwerte eingehalten werden.There is also a need to reduce the nitrogen oxide content to such an extent that the legal limit values are observed.
Derzeit erfolgt die Verminderung des Stickstoffoxidgehaltes durch Reduktion mit Ammoniak an teuren Katalysatoren. Dieses Verfahren ist teuer und erfordert einen eigenen Anlagenteil.The nitrogen oxide content is currently reduced by reduction with ammonia over expensive catalysts. This process is expensive and requires its own part of the plant.
Aufgabe der Erfindung ist, die vorstehend aufgeführten Bedürfnisse zu befriedigen und ein hierfür geeignetes Mittel zur Verfügung zu stellen.The object of the invention is to satisfy the needs listed above and to provide a suitable means.
Gelöst wird diese Aufgabe gemäß der Erfindung durch ein Mittel, welches aus - Gruppe A: porösen, säurebeständigen, anorganischen Stoffen;This object is achieved according to the invention by an agent which consists of - Group A: porous, acid-resistant, inorganic substances;
- Gruppe B: anorganischen und/oder organischen Säuren, die in den porösen, säurebeständigen, anorganischen Stoffen aufgesaugt vorliegen;Group B: inorganic and / or organic acids which are absorbed in the porous, acid-resistant, inorganic substances;
- Gruppe C: oberflächenaktiven Substanzen und - Gruppe D: basischen Stoffen, wobei die Vertreter der Gruppen A, B und C immer vorliegen müssen, diejenigen der Gruppe D dagegen wahlweise eingesetzt werden, besteht.- Group C: surface-active substances and - Group D: basic substances, where the representatives of groups A, B and C must always be present, whereas those of group D are used alternatively.
Im Wesen beruht die Erfindung darauf, gefunden zu haben, dass die Abscheideleistung der bekannten oberflächenaktiven Substanzen durchIn essence, the invention is based on having found that the separation performance of the known surface-active substances is achieved by
Beaufschlagung mit Säuren, die in porösen, säurebeständigen, anorganischen Stoffen aufgesaugt sind und während des Abscheideverfahrens zusammen mit den oberflächenaktiven Substanzen aktiv werden, verbessert werden kann.Exposure to acids, which are absorbed in porous, acid-resistant, inorganic substances and during the The deposition process together with the surface-active substances can be improved.
Mit dem vorgeschlagenen Mittel lassen sich überraschend und unerwartet die gestellten Aufgaben lösen.The proposed means surprisingly and unexpectedly solve the tasks.
Als Vertreter der Gruppe A sind in pulvriger oder gekörnter Form gebrannte Tone, Kieselgur, Perlite, Bimsstein, Blähton, Gasbeton, Aluminiumoxid und/oder Kieselgel geeignet. Es handelt sich bei diesen Substanzen um hochoxidierte Verbindungen, die aufgrund ihrer Herstellung sowohl gegen Säuren stabil sind als auch über ein bestimmtes Säure-Porenvolumen für die angeführten Säuren verfügen.Fired clays, diatomaceous earth, perlite, pumice stone, expanded clay, gas concrete, aluminum oxide and / or silica gel are suitable as representatives of group A in powdered or granular form. These substances are highly oxidized compounds which, due to their production, are both stable against acids and have a certain acid pore volume for the acids mentioned.
Das Säure-Porenvolumen wird dadurch bestimmt, dass zu 1 g der Säure solange feinpulvriges, poröses, säurebeständiges, anorganisches Material gegeben wird, bis ein trockenes Pulver erhalten wird. Im Falle von konzentrierter Schwefelsäure besteht bei Ziegelmehl das trockene Gemisch aus 75 Gew.-% Ziegelmehl und 25 Gew.-% Schwefelsäure, im Falle von Kieselgur aus 52 Gew.-% Kieselgur und 48 Gew.-% Schwefelsäure.The acid pore volume is determined by adding fine powder, porous, acid-resistant, inorganic material to 1 g of the acid until a dry powder is obtained. In the case of concentrated sulfuric acid, the dry mixture of brick powder consists of 75% by weight brick powder and 25% by weight sulfuric acid, in the case of diatomaceous earth it consists of 52% by weight kieselguhr and 48% by weight sulfuric acid.
Auf diese einfache Weise lässt sich für alle angeführten Stoffe und auch für alle Säuren das Säure-Porenvolumen bestimmen.In this simple way, the acid-pore volume can be determined for all substances listed and also for all acids.
Für das Flugstromverfahren ist es unbedingt erforderlich, dass absolut staubförmiges Gemische aus den porösen Stoffen und den Säuren vorliegen.For the entrained current process, it is absolutely essential that absolutely dust-like mixtures of the porous substances and the acids are present.
Als anorganische oder organische Säuren, die in dem porösen, säurebeständigen, anorganischen Stoffen aufgesaugt vorliegen, zählen Schwefelsäure, Salzsäure, Salpetersäure, Essigsäure und Ameisensäure. Von den aufgeführten Säuren ist Schwefelsäure bevorzugt. Schwefelsäure wirkt sowohl als Säure als auch als stark oxidierendes Mittel bei den Temperaturen der Abgasreinigung. Dies bedeutet, dass O-wertiges Quecksilber zu 1 - oder 2-wertigem Quecksilber oxidiert wird. Die Oxidation erfolgt hierbei entweder im Gasraum oder an den oberflächenaktiven Substanzen, an denen sich auch Schwefelsäure niederschlägt. Es werden hierbei nicht nur flüchtige Schwermetalle oxidiert, sondern auch organische Schadstoffe, wie insbesondere chlorierte Dioxine und Furane, chlorierte aromatische und aliphatische Kohlenwasserstoffe, chloriertes Biphenylen, aromatische Kohlenwasserstoffe und andere toxische organische Verbindungen.The inorganic or organic acids which are absorbed in the porous, acid-resistant, inorganic substances include sulfuric acid, hydrochloric acid, nitric acid, acetic acid and formic acid. Of the acids listed, sulfuric acid is preferred. Sulfuric acid acts both as an acid and as a strong oxidizing agent in the Exhaust gas cleaning temperatures. This means that O-valent mercury is oxidized to 1- or 2-valent mercury. The oxidation takes place either in the gas space or on the surface-active substances, on which sulfuric acid is also deposited. Not only are volatile heavy metals oxidized, but also organic pollutants, such as especially chlorinated dioxins and furans, chlorinated aromatic and aliphatic hydrocarbons, chlorinated biphenyls, aromatic hydrocarbons and other toxic organic compounds.
Der Vorteil dieser Mittel besteht nun darin, dass diese Schadstoffe nicht nur an den oberflächenaktiven Substanzen adsorbiert werden, sondern durch Einwirkung der Schwefelsäure zersetzt und oxidiert werden. Damit sind auch die erhaltenen Endprodukte ganz oder weitestgehend frei von diesen gefährlichen Schadstoffen.The advantage of these agents is that these pollutants are not only adsorbed on the surface-active substances, but are decomposed and oxidized by the action of sulfuric acid. This means that the end products obtained are completely or largely free of these dangerous pollutants.
Eine ähnliche Wirkung wie Schwefelsäure hat auch Salpetersäure, die neben ihrer sauren Wirkung auch noch oxidierende Eigenschaften aufweist.Nitric acid has a similar effect to that of sulfuric acid, which in addition to its acidic effect also has oxidizing properties.
Salzsäure, Essigsäure und Ameisensäure sind nicht oxidierend und verstärken deshalb im Wesentlichen die Abscheidung von flüchtigen Schwermetallen, insbesondere von Quecksilber, auch in elementarer Form, überraschend auf den angeführten oberflächenaktiven Substanzen.Hydrochloric acid, acetic acid and formic acid are not oxidizing and therefore essentially increase the separation of volatile heavy metals, especially mercury, even in elemental form, surprisingly on the surface-active substances mentioned.
Als oberflächenaktive Substanzen sind Aktivkohlen der verschiedensten Herstellung, Braunkohlen-Herdofenkoks (nachfolgend nur als Herdofenkoks, bzw. HOK bezeichnet), aktiviertes Aluminiumoxid und/oder Kieselgel geeignet. Es ist bekannt, dass die Aktivkohlen und auch Herdofenkoks besonders zur Abscheidung von organischen Stoffen und flüchtigen Schwermetallen geeignet sind. Allerdings besteht bei diesen rein kohlenstoffhaltigen Substanzen immer die Gefahr des Auftretens von Glimmbränden. Insofern ist es angebrcht, bei brandkritischen Situationen Aluminiumoxid oder Kieselgel einzusetzen.Activated carbons of the most varied production, brown coal hearth coke (hereinafter referred to only as hearth coke or HOK), activated aluminum oxide and / or silica gel are suitable as surface-active substances. It is known that the activated carbons and also hearth furnace coke are particularly suitable for the separation of organic substances and volatile heavy metals. However, there is always a risk of the occurrence of these purely carbon-containing substances Smoldering. It is therefore appropriate to use aluminum oxide or silica gel in fire-critical situations.
Um das Austreten von Säuren in das Reingas zu verhindern, kann es angebracht sein, basische Stoffe zuzusetzen. Bevorzugt werden als basische Stoffe Calciumhydroxid, Calciumcarbonat, Branntkalk, Dolomit, Natriumcarbonat und/oder Natriumhydrogencarbonat. Mit den angeführten basischen Substanzen lassen sich auch die sauren Bestandteile der Abgase, Chlorwasserstoff, Schwefeldioxid und Fluorwasserstoff abscheiden.In order to prevent acids from escaping into the clean gas, it may be appropriate to add basic substances. Calcium hydroxide, calcium carbonate, quicklime, dolomite, sodium carbonate and / or sodium hydrogen carbonate are preferred as basic substances. The acidic components of the exhaust gases, hydrogen chloride, sulfur dioxide and hydrogen fluoride can also be separated with the basic substances listed.
Das erfindungsgemäße Mittel bildet ein universelles System zur hervorragenden Abscheidung von flüchtigen Schwermetallen und organischen Schadstoffen sowie auch von Stickstoffoxiden, insbesondere Stickstoffmonoxid.The agent according to the invention forms a universal system for the excellent separation of volatile heavy metals and organic pollutants and also of nitrogen oxides, in particular nitrogen monoxide.
Zur äußeren Form des Mittels ist festzustellen, dass es entweder in pulvriger Form oder als Granulat vorliegt. In pulvriger Form mit einer Korngröße < 1 00 μm, vorzugsweise < 50 μm, bevorzugt < 10 //m, dient es als Adsorbens im Flugstromverfahren. Wird jedoch in Festbettschicht gearbeitet, dann ist es zweckmäßig, das Mittel als Granulat einzusetzen. Die Korngröße liegt hierbei zwischen 1 und 10 mm, bevorzugt zwischen 2 und 5 mm.Regarding the external form of the product, it should be noted that it is either in powder form or as granules. In powdery form with a grain size <100 μm, preferably <50 μm, preferably <10 // m, it serves as an adsorbent in the entrained flow process. However, if you work in a fixed bed layer, it is advisable to use the agent as granules. The grain size is between 1 and 10 mm, preferably between 2 and 5 mm.
Die einzelnen Komponenten werden zweckmäßig in ihrer Körnung so abgestimmt, dass bei Einsatz eines Gemisches keine Entmischung eintreten kann. Dies gilt insbesondere beim Einsatz von staubförmigen Mitteln, bei denen durch die im Abgas verursachten Turbulenzen die Möglichkeit der Entmischung besteht.The granularity of the individual components is appropriately coordinated so that no segregation can occur when a mixture is used. This applies in particular to the use of dust-like agents in which there is a possibility of segregation due to the turbulence caused in the exhaust gas.
Die Säuren können in wässriger Lösung beliebiger Konzentration oder auch im Falle von Schwefelsäure, Essigsäure und Ameisensäure in wasserfreier Form aufgesaugt in den porösen anorganischen Stoffen vorliegen. Insbesondere bei Schwefelsäure empfiehlt es sich mit konzentrierter Schwefeläsure zu arbeiten, da der Bedarf an porösen anorganischen Stoffen gering ist und die oxidierende Wirkung der Schwefelsäure höher ist.The acids can be present in the porous inorganic substances in an aqueous solution of any concentration or, in the case of sulfuric acid, acetic acid and formic acid, in an anhydrous form. In the case of sulfuric acid in particular, it is advisable to work with concentrated sulfuric acid, since the need for porous inorganic substances is low and the oxidizing effect of sulfuric acid is higher.
Ein bevorzugtes Mittel besteht aus porösem Ziegelmehl und/oder Kieselgur mit aufgesaugter Schwefelsäure, Salpetersäure und/oder Salzsäure und Aktivkohle und/oder Herdofenkoks und Caiciumhydroxid und/oder Calciumcarbonat.A preferred agent consists of porous brick powder and / or diatomaceous earth with absorbed sulfuric acid, nitric acid and / or hydrochloric acid and activated carbon and / or hearth furnace coke and calcium hydroxide and / or calcium carbonate.
Insbesondere bei der Verwendung von Schwefelsäure können mit dem bevorzugten Mittel sowohl die flüchtigen Schwermetalle gut abgeschieden werden als auch die zahlreichen organischen Schadstoffe und weiterhin auch noch Stickstoffoxide in ihrem Gehalt erheblich vermindert werden. Durch die Anwesenheit von Caiciumhydroxid und/oder Calciuimcarbonat kommt es auch zu einer ausreichenden Verminderung des Gehaltes an Chlorwasserstoff und Schwefeldioxid des Abgases.In particular when using sulfuric acid, the preferred agent can both separate the volatile heavy metals well and also significantly reduce the content of numerous organic pollutants and also nitrogen oxides. The presence of calcium hydroxide and / or calcium carbonate also leads to a sufficient reduction in the content of hydrogen chloride and sulfur dioxide in the exhaust gas.
Die Mengen der einzelnen Komponenten können im erfindungsgemäßen Mittel im weiten Bereich variiert werden. Soll das Mittel zur Abgasreinigung bei Müllverbrennungsanlagen eingesetzt werden und zwar in einem 1 - stufigen Verfahren, dann richtet sich der Gehalt an basischen Stoffen, vornehmlich Caiciumhydroxid, nach dem Gehalt an Chlorwasserstoff und Schwefeldioxid. Der Gehalt beträgt dann bevorzugt 45-98 Gew.-% an basischen Stoffen. Die oberflächenaktiven Substanzen weisen bevorzugt einen Gehalt von 1 bis 50 Gew.-% auf, während die Gruppe A mit den aufgesaugten Säuren bevorzugt einen Anteil von 1 bis 5 Gew.-% hat. Die Menge der aufgesaugten Säure reicht bei diesem Anteil an porösen, anorganischen, säurebeständigen Stoffen völlig aus, die flüchtigen Schwermetalle, insbesondere das 0-wertige Quecksilber und auch die organischen Stoffe zu oxidieren. Außerdem kann der Anteil an Stickstoffoxiden noch deutlich vermindert werden. In einer weiteren bevorzugten Ausführungsform besteht das Mittel aus porösem Ziegelmehl und/oder Kieselgur mit aufgesaugter Schwefelsäure, Salpetersäure und/oder Salzsäure und Aktivkohle und/oder Herdofenkoks. In dieser Form findet das Mittel zur Nachreinigung von Abgasen Anwendung, die bereits einem Reinigungsverfahren, sei es im Flugstromverfahren in trockener Ausführungoder im Nassverfahren, vorgereinigt worden sind. Da der Hauptteil der sauren Bestandteile, Chlorwasserstoff und Schwefeldioxid, bereits entfernt worden ist, kann auf die Anwesenheit der basischen Stoffe verzichtet werden.The amounts of the individual components can be varied within a wide range in the agent according to the invention. If the waste gas cleaning agent is to be used in waste incineration plants in a one-stage process, the content of basic substances, primarily calcium hydroxide, depends on the content of hydrogen chloride and sulfur dioxide. The content is then preferably 45-98% by weight of basic substances. The surface-active substances preferably have a content of 1 to 50% by weight, while group A with the absorbed acids preferably has a proportion of 1 to 5% by weight. With this proportion of porous, inorganic, acid-resistant substances, the amount of acid absorbed is sufficient to oxidize the volatile heavy metals, especially the 0-valent mercury and also the organic substances. In addition, the proportion of nitrogen oxides can be significantly reduced. In a further preferred embodiment, the agent consists of porous brick powder and / or diatomaceous earth with absorbed sulfuric acid, nitric acid and / or hydrochloric acid and activated carbon and / or hearth furnace coke. In this form, the agent is used to purify exhaust gases that have already been pre-cleaned in a cleaning process, be it in the entrained flow process in a dry version or in the wet process. Since the majority of the acidic components, hydrogen chloride and sulfur dioxide, have already been removed, the presence of the basic substances can be dispensed with.
Eine weitere Anwendung ist gegeben, wenn die zu reinigenden Gase säurefrei sind. Um sicher zu gehen, dass keine Säuren ins Reingas gelangen, können die basischen Mittel in geringer Menge zugegeben werden. Ausreichend ist die Menge, die zur Neutralisation der eingebrachten Menge Säuren, erforderlich ist.Another application is when the gases to be cleaned are acid-free. To ensure that no acids get into the clean gas, the basic agents can be added in small amounts. The amount required to neutralize the amount of acids introduced is sufficient.
Das Mittel besteht in diesem Falle aus 1 bis 1 0 Gew.-% eines Vertreters der Gruppe A mit aufgesaugten Säuren und 90 bis 99 Gew.-% von Vertretern der Gruppe C, also der oberflächenaktiven Substanzen.In this case, the composition consists of 1 to 10% by weight of a representative of group A with absorbed acids and 90 to 99% by weight of representatives of group C, that is to say the surface-active substances.
Die erfindungsgemäßen Mittel können nach dem erfindungsgemäßen Verfahren dadurch hergestellt werden, dass die Vertreter der aufgeführten Komponenten trocken gemischt werden. Dies geschieht zweckmäßigerweise dadurch, dass zu den Säuren so große Mengen an Vertretern der Gruppe A, d.h. der porösen, säurebeständigen, anorganischen Stoffen zugegeben werden, bis ein Pulver mit den üblichen Fließ-, Riesel- und Flugeigenschaften entsteht. Dieses Gemisch aus Vertretern der Gruppe A und der Gruppe B wird dann mit den ebenfalls pulverförmigen und trockenen Vertretern der Gruppe C und wahlweise auch mit D gemischt. Es liegt dann ein leicht zu handhabendes pulverförmiges Gemisch vor, das für das Flugstromverfahren eingesetzt werden kann. Das erfindungsgemäße Mittel kann auch als Granulat vorliegen. In diesem Falle wird aus den Vertretern der Gruppe C und D auf bekanntem Wege ein Granulat hergestellt, deren Korngröße im Bereich von 1 bis 1 0 mm, vorzugsweise 2 bis 5 mm, liegt. Zu diesem Granulat wird nun gekörntes Material der Gruppe A gegeben, das die Säuren aufgesaugt enthält. Diese Mischung aus granuliertem und gekörntem Material kann dann für die Abgasreinigung im Festbett eingesetzt werden.The agents according to the invention can be prepared by the method according to the invention in that the representatives of the listed components are mixed dry. This is expediently done by adding large amounts of representatives of group A, ie the porous, acid-resistant, inorganic substances, to the acids until a powder with the usual flow, flow and flight properties is obtained. This mixture of representatives of group A and group B is then mixed with the likewise powdery and dry representatives of group C and optionally also with D. There is then an easy-to-use powdery mixture that can be used for the entrained-flow process. The agent according to the invention can also be present as granules. In this case, the representatives of groups C and D are produced in a known manner into granules whose grain size is in the range from 1 to 10 mm, preferably 2 to 5 mm. Granular material from group A, which contains the acids, is now added to these granules. This mixture of granulated and granular material can then be used for exhaust gas cleaning in a fixed bed.
Wird auf die Gruppe D, d.h. die basischen Materialien verzichtet, dann wird eine Mischung aus gekörnten oberflächenaktiven Substanzen und gekörntem Material der Gruppe A, das die Säuren aufgesaugt enthält, hergestellt.Is group D, i.e. dispenses with the basic materials, then a mixture of granular surface-active substances and granular material from group A, which contains the acids, is prepared.
Das Mittel nach den Ansprüchen 1 bis 9 wird erfindungsgemäß zur Entfernung von flüchtigen Schwermetallen, insbesondere elementaren Schwermetallen, chlorierten Dioxinen und Furanen, chlorierten aromatischen und aliphatischen Kohlenwasserstoffen, chlorierten Biphenylen, aromatischen Kkohlenwasserstoffen, toxischen organischen Verbindungen, Chlorwasserstoff und/oder Schwefeldioxid und Stickstoffoxiden aus Gasen, insbesondere Abgasen, eingesetzt, indem es in den Gasstrom eingebrcht, schädliche Inhaltsstoffe des Gases mit dem Mittel bei einer Temperatur von 20 bis 400 °C, insbesondere 60 bis 250 °C, vorzugsweise 1 20 bis 210 °C, behandelt und die Reaktionsprodukte sowie nicht umgesetztes Mittel an Gewebefiltern oder Elektrofiltern abgeschieden werden.The agent according to claims 1 to 9 is used according to the invention to remove volatile heavy metals, in particular elemental heavy metals, chlorinated dioxins and furans, chlorinated aromatic and aliphatic hydrocarbons, chlorinated biphenyls, aromatic hydrocarbons, toxic organic compounds, hydrogen chloride and / or sulfur dioxide and nitrogen oxides from gases , in particular exhaust gases, used by breaking into the gas stream, treating harmful constituents of the gas with the agent at a temperature of 20 to 400 ° C., in particular 60 to 250 ° C., preferably 1 20 to 210 ° C., and the reaction products as well unreacted agent can be separated on fabric filters or electrostatic filters.
Dieses Verfahren besteht darin, dass das pulverförmige Material auf bekannte Weise in den Abgasstrom eingedüst, in diesem verwirbelt und anschließend die Feststoffe an einem auf ein Gewebefilter oder ein Elektrofilter aufgetragen werden.This method consists in that the pulverulent material is injected into the exhaust gas stream in a known manner, swirled in the latter and then the solids are applied to a fabric filter or an electrostatic filter.
Die Temperatur muss hierbei so hoch sein, dass es nicht zu Kondensationen von Wasser auf dem erfindungsgemäßen Mittel kommt. Im Allgemeinen wird hierzu eine Temperatur mit 30 °C oberhalb des Taupunktes des Gases gewählt.The temperature must be so high that there is no condensation of water on the agent according to the invention. In general a temperature of 30 ° C above the dew point of the gas is selected.
Es besteht jedoch auch die Möglichkeit, die Komponenten des Mittels getrennt voneinander, gleichzeitig oder in beliebiger Reihenfolge nacheinander in den zu reinigenden Abgasstrom eingebracht werden. Bevorzugt werden hierbei die Vertreter der Gruppe A, die die Säuren aufgesaugt enthalten, und die oberflächenaktiven Substanzen zuerst eindosiert und dann erst die basischen Substanzen.However, there is also the possibility of introducing the components of the agent separately from one another, simultaneously or in any order into the exhaust gas stream to be cleaned. The representatives of group A, which contain the acids soaked up, and the surface-active substances are first metered in and only then the basic substances.
Wird bei dem erfindungsgemäßen Verfahren mit einem Festbettfilter gearbeitet, dann ergeben sich die gleichen Temperaturen und die gleichen Randbedingungen wie beim Flugstromverfahren unter Eindüsung der pulverförmigen Mittel in den Abgasstrom.If a fixed bed filter is used in the method according to the invention, the same temperatures and the same boundary conditions result as in the entrained flow method while the powdery agents are injected into the exhaust gas stream.
Bevorzugt wird das Mittel bei der Trockensorption, der konditionierten Trockensorption und der Sprühsorption eingesetzt. Je nach Aufbau des Reinigungsverfahrens kann das Mittel an verschiedenen Stellen der Abgasreinigungsanlage in den Gasstrom eingebracht werden. Vorzugsweise erfolgt die Zugabe als Gemisch aller Substanzen.The agent is preferably used in dry sorption, conditioned dry sorption and spray sorption. Depending on the structure of the cleaning process, the agent can be introduced into the gas stream at various points in the exhaust gas cleaning system. The addition is preferably carried out as a mixture of all substances.
Bei der Sprühsorption muss so verfahren werden, dass das Mittel ohne die basischen Komponenten der Gruppe D erst nach Durchführung des Trocknungsvorganges zugegeben werden kann. Das heißt, eingesetzt wird ein Mittel aus den Vertretern der Gruppe A, die die Säuren aufgesaugt enthalten, und Vertretern der Gruppe C, der oberflächenaktiven Substanzen.Spray sorption must be carried out in such a way that the agent can only be added without the basic components of group D after the drying process has been carried out. That is, an agent is used from the representatives of group A, which contain the acids, and representatives of group C, the surface-active substances.
Auf die Zugabe der basischen Mittel kann verzichtet werden, da die Sprühsorption bekanntermaßen mit Kalkmilch arbeitet.The addition of the basic agents can be dispensed with, since spray sorption is known to work with milk of lime.
Ebenfalls ohne basische Substanzen oder nur einer geringen Menge davon kann gearbeitet werden, wenn das Mittel nach der Nasswäsche der Abgase eingesetzt wird. Hierbei ist allerdings darauf zu achten, dass der Abstand zum Taupunkt des Gases mehr als 30 °C beträgt.You can also work without basic substances or only a small amount of it if the agent after the wet scrubbing of the exhaust gases is used. However, it must be ensured that the distance to the dew point of the gas is more than 30 ° C.
Beispiele: Beispiel 1 - VergleichsbeispielExamples: Example 1 - comparative example
Über 250 mg eines Gemisches aus 240 mg Ca(OH)2 und 10 mg Braunkohlen-Herdofenkoks (HOK) wurden bei 1 80 °C 27 I des folgenden Gases geleitet:Over 250 mg of a mixture of 240 mg of Ca (OH) 2 and 10 mg of lignite hearth coke (HOK) were passed at 1 80 ° C 27 l of the following gas:
- Stickstoff 90 Vol.-% - Sauerstoff 1 0 Vol.-%- nitrogen 90 vol .-% - oxygen 1 0 vol .-%
- HCI 1 8, 1 mg/l- HCI 1.8, 1 mg / l
- Feuchte 0, 1 5 g/l- Moisture 0.15 g / l
- Hg als (HgCI2) 0,3 μg/l- Hg as (HgCI2) 0.3 μg / l
Von insgesamt 8, 1 μg eindosiertem Quecksilber wurden 2,3 μg wiedergefunden. Dies bedeutet eine Quecksilberabscheidung 71 ,6 %.Of a total of 8.1 μg of mercury metered in, 2.3 μg were recovered. This means a mercury separation of 71.6%.
Beispiel 2 - VergleichsbeispielExample 2 - Comparative Example
1 g reine, wasserfreie Schwefelsäure (H2SO4) wurde mit 3 g Ziegelmehl - Körnung 1 00 % < 45 μm vermischt. Es entstand ein trockenes Pulver, das keine Verbackungstendenz zeigte.1 g of pure, anhydrous sulfuric acid (H 2 SO 4 ) was mixed with 3 g of brick flour grain size 1 00% <45 μm. A dry powder was formed which showed no tendency to cake.
Aus Caiciumhydroxid (Ca(OH2) und diesem Ziegelmehl/Schwefelsäure- Gemisch wurde ein Gemisch aus 98 Gew.-% Ca(OH)2 und 2 Gew.-% Ziegelmehl/Schwefelsäure-Pulver hergestellt.A mixture of 98% by weight Ca (OH) 2 and 2% by weight brick powder / sulfuric acid powder was prepared from calcium hydroxide (Ca (OH 2 ) and this brick powder / sulfuric acid mixture.
Über 250 mg dieses Gemisches wurden bei 1 80 °C 27 I des Gasgemisches aus Beispiel 1 geleitet.About 250 mg of this mixture were passed at 1 80 ° C 27 I of the gas mixture from Example 1.
Von insgesamt 8, 1 μg eindosiertem Quecksilber wurden 5,8 μg wiedergefunden. Dies bedeutet eine Quecksilberabscheidung von 28,4 %. Beispiel 3Of a total of 8.1 μg of mercury metered in, 5.8 μg were recovered. This means a mercury separation of 28.4%. Example 3
Cas Ca(OH)2, HOK und Ziegelmehl/Schwefelsäure-Pulver wurde eineCas Ca (OH) 2 , HOK and brick flour / sulfuric acid powder became one
Adsorbens folgender Zusammensetzung hergestellt.Adsorbent produced the following composition.
- 235 mg Ca(OH)2, 94 Gew.-% - 1 0 mg HOK, 4 Gew.-%- 235 mg Ca (OH) 2, 94 wt .-% - 1 0 mg HOK, 4 wt .-%
- 5 mg Ziegelmehl/Schwefelsäure-Pulver, 2 Gew.-%, Schwefelsäure, 0,5 Gew.-%- 5 mg brick powder / sulfuric acid powder, 2% by weight, sulfuric acid, 0.5% by weight
Über 250 mg dieses Gemisches wurden bei 1 80 °C 27 I des Gasgemisches aus Beispiel 1 geleitet.About 250 mg of this mixture were passed at 1 80 ° C 27 I of the gas mixture from Example 1.
Von insgesamt 8, 1 μg eindosiertem Quecksilber wurden 0,3 μg wiedergefunden. Dies bedeutet eine Quecksilberabscheidung 96,3 %.Of a total of 8.1 μg of mercury metered in, 0.3 μg was recovered. This means a mercury separation of 96.3%.
Ein Vergleich der Beispiele zeigt, dass durch die Zugabe von Schwefelsäure in Ziegelmehl zum basischen Gemisch aus Ca(OH)2 und HOK eine erhebliche unerwartete Verbesserung der Quecksilberabscheidung erzielt werden kann.A comparison of the examples shows that the addition of sulfuric acid in brick flour to the basic mixture of Ca (OH) 2 and HOK can achieve a significant unexpected improvement in mercury separation.
Eine derartige Abscheidung kann mit säurefreien Adsorbentien nur dann erreicht werden, wenn der Anteil von HOK auf 1 0 Gew.-% erhöht wird, also um 1 50 %! Such a separation can only be achieved with acid-free adsorbents if the proportion of HOK is increased to 1 0% by weight, ie by 1 50%!

Claims

Ansprüche Expectations
1. Mittel zur Reinigung von Gasen und Abgasen, bestehend aus - Gruppe A: porösen, säurebeständigen, anorganischen Stoffen,1. Agents for cleaning gases and exhaust gases, consisting of - Group A: porous, acid-resistant, inorganic substances,
Gruppe B: anorganischen und/oder organischen Säuren, die in den porösen, säurebeständigen, anorganischen Stoffen aufgesaugt vorliegen,Group B: inorganic and / or organic acids which are absorbed in the porous, acid-resistant, inorganic substances,
Gruppe C: oberflächenaktiven Substanzen und gegebenenfalls - Gruppe D: basischen Stoffen.Group C: surface-active substances and optionally - Group D: basic substances.
2. Mittel nach Anspruch 1, d a d u rc h g e ke n n ze i c h n et , dass es als Vertreter der Gruppe A in pulvriger oder gekörnter Form gebrannte Tone, Kieselgur, Perlite, Bimsstein, Blähton, Gasbeton,2. Means according to claim 1, d a d u rc h g e ke n n ze i c h n et that it as a representative of group A fired clays in powdery or granular form, diatomaceous earth, perlite, pumice, expanded clay, gas concrete,
Aluminiumoxid und/oder Kieselgel, als Vertreter der Gruppe B Schwefelsäure, Salzsäure, Salpetersäure, Essigsäure und/oder Ameisensäure in beliebiger Konzentration, als Vertreter der Gruppe C Aktivkohlen, Herdofenkoks, aktiviertes Aluminiumoxid und/oder Kieselgel und als Vertreter der Gruppe D Caiciumhydroxid, Calciumcarbonat, Branntkalk, Dolomit, Natriumcarbonat und/oder Natriumhydrogencarbonat enthält.Aluminum oxide and / or silica gel, as representatives of group B sulfuric acid, hydrochloric acid, nitric acid, acetic acid and / or formic acid in any concentration, as representatives of group C activated carbons, hearth coke, activated aluminum oxide and / or silica gel and as representatives of group D calcium hydroxide, calcium carbonate , Quicklime, dolomite, sodium carbonate and / or sodium hydrogen carbonate.
3. Mittel nach einem der vorhergehenden Ansprüche, d a d u rc h g e ke n n ze i c h n et, dass die Vertreter der Gruppe A, C und D in feinpulvriger Form oder als Granulat vorliegen.3. Means according to one of the preceding claims, that the representatives of groups A, C and D are present in finely powdered form or as granules.
4. Mittel nach einem der vorhergehenden Ansprüche, d a d u rc h g e ke n n ze i c h n et , dass die feinpulvrigen Substanzen eine Korngröße von < 1 00 μm, vorzugsweise < 50 μm, bevorzugt < 10 μm aufweisen und die Korngröße der Granulate im Bereich von 1 bis 1 0 mm, vorzugsweise 2 bis 5 mm liegt.4. Means according to one of the preceding claims, dadu rc hge ke nn ze ichn et, that the fine powdery substances have a grain size of <100 μm, preferably <50 μm, preferably <10 μm and the grain size of the granules is in the range from 1 to 10 mm, preferably 2 to 5 mm.
5. Mittel nach einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass die ausgewählten Säuren in wässriger Lösung beliebiger Konzentration oder im Falle von Schwefelsäure, Essigsäure und Ameisensäure auch in wasserfreier Form vorliegen.5. Composition according to one of the preceding claims, that the selected acids are present in aqueous solution of any concentration or, in the case of sulfuric acid, acetic acid and formic acid, also in anhydrous form.
6. Mittel nach einem der vorhergehenden Ansprüche bestehend im Wesentlichen aus porösem Ziegelmehl und/oder Kieselgur mit aufgesaugter Schwefelsäure, Salpetersäure und/oder Salzsäure und Aktivkohle und/oder Herdofenkoks.6. Composition according to one of the preceding claims consisting essentially of porous brick powder and / or diatomaceous earth with absorbed sulfuric acid, nitric acid and / or hydrochloric acid and activated carbon and / or hearth furnace coke.
7. Mittel nach Anspruch 6, bestehend im Wesentlichen aus 1 bis 10 Gew.-% eines Vertreters der Gruppe A mit aufgesaugten Säuren der Gruppe B und 90 bis 99 Gew.-% von Vertretern der Gruppe C.7. Composition according to claim 6, consisting essentially of 1 to 10 wt .-% of a representative of group A with absorbed acids of group B and 90 to 99 wt .-% of representatives of group C.
8. Mittel nach einem der Ansprüche 1 bis 5, bestehend im Wesentlichen aus porösem Ziegelmehl und/oder Kieselgur mit aufgesaugter Schwefelsäure, Salpetersäure und/oder Salzsäure und Aktivkohle und/oder Herdofenkoks und Caiciumhydroxid und/oder Calciumcarbonat.8. Composition according to one of claims 1 to 5, consisting essentially of porous brick powder and / or diatomaceous earth with absorbed sulfuric acid, nitric acid and / or hydrochloric acid and activated carbon and / or hearth furnace coke and calcium hydroxide and / or calcium carbonate.
9. Mittel nach Anspruch 8, bestehend im Wesentlichen aus 1 bis 5 Gew.-% von Vertretern der Gruppe A mit aufgesaugten Säuren der Gruppe B, 1 bis 50 Gew.-% an oberflächenaktiven Substanzen und 45 bis 98 Gew.-% basischer Stoffe. 9. Composition according to claim 8, consisting essentially of 1 to 5 wt .-% of representatives of group A with absorbed acids of group B, 1 to 50 wt .-% of surface-active substances and 45 to 98 wt .-% basic substances .
10. Verfahren zur Herstellung eines Mittels nach einem der Ansprüche 1 bis 9, d a d u r c h g e ke n n z e i c h n et , dass die Vertreter der aufgeführten Komponenten trocken gemischt oder getrennt in einen zu reinigenden Gasstrom eingedüst und dort in situ gemischt werden.10. A process for the preparation of an agent according to any one of claims 1 to 9, that the representatives of the listed components are mixed dry or injected separately into a gas stream to be cleaned and mixed there in situ.
11. Verfahren zur Herstellung eines Mittels nach einem der Ansprüche 1 bis 9 als Granulat, d a d u rch g e ken nzei c h n et, dass aus den Vertretern der Gruppe C und der Gruppe D ein Granulat hergestellt wird und dieses mit gekörntem Material der Gruppe A, das die Säuren aufgesaugt enthält, gemischt wird.11. A process for the preparation of an agent according to any one of claims 1 to 9 as granules, dadu rch ge ken nzei chn et that from the representatives of group C and group D a granulate is produced and this with granular material of group A, the which contains acids absorbed, is mixed.
12. Verfahren zur Entfernung von flüchtigen Schwermetalien, insbesondere elementaren Schwermetallen, chlorierten Dioxinen und Furanen, chlorierten aromatischen und aliphatischen Kohlenwasserstoffen, chlorierten Biphenylen, aromatischen Kohlenwasserstoffen, toxischen organischen Verbindungen, Chlorwasserstoff und/oder Schwefeldioxid und Stickstoffoxiden aus12. A process for removing volatile heavy metals, in particular elemental heavy metals, chlorinated dioxins and furans, chlorinated aromatic and aliphatic hydrocarbons, chlorinated biphenyls, aromatic hydrocarbons, toxic organic compounds, hydrogen chloride and / or sulfur dioxide and nitrogen oxides
Gasen, insbesondere Abgasen, d a d u rc h g e ke n n ze i c h n et, dass ein Mittel nach einem der Ansprüche 1 bis 9 in den Gasstrom eingebracht, die schädlichen Inhaltsstoffe des Gases mit dem Mittel bei einer Temperatur von 20 bis 400 °C, insbesondere 60 bis 250Gases, in particular exhaust gases, so that an agent according to one of claims 1 to 9 is introduced into the gas stream, the harmful constituents of the gas with the agent at a temperature of 20 to 400 ° C, in particular 60 to 250
°C, vorzugsweise 120 bis 210 °C, behandelt und die Reaktionsprodukte sowie nicht umgesetztes Mittel an Gewebefiltern oder Elektrofiltern abgeschieden werden.° C, preferably 120 to 210 ° C, treated and the reaction products and unreacted agent are separated on fabric filters or electrostatic filters.
13. Verfahren nach Anspruch 12, d a d u r c h g e ke n n ze i c h n et , dass die Komponenten des Mittels als Gemisch oder getrennt, gleichzeitig oder in beliebiger Reihenfolge nacheinander, in den zu reinigenden Abgasstrom eingebracht werden.13. The method according to claim 12, dadurchge ke nn ze ichn et, that the components of the agent are introduced into the exhaust gas stream to be cleaned as a mixture or separately, simultaneously or in any order one after the other.
14. Verfahren zur Entfernung von flüchtigen Schwermetallen, insbesondere elementaren Schwermetallen, chlorierten Dioxinen und Furanen, chlorierten aromatischen und aliphatischen Kohlenwasserstoffen, chlorierten Biphenylen, aromatischen Kohlenwasserstoffen, toxischen organischen Verbindungen, Chlorwasserstoff und/oder Schwefeldioxid und Stickstoffoxiden aus14. A process for removing volatile heavy metals, especially elemental heavy metals, chlorinated dioxins and furans, chlorinated aromatic and aliphatic hydrocarbons, chlorinated biphenyls, aromatic hydrocarbons, toxic organic compounds, hydrogen chloride and / or sulfur dioxide and nitrogen oxides
Gasen, insbesondere Abgasen, d a d u rc h g e ke n n z e i c h n et , dass der zu behandelnde Gasstrom durch eine Granulatschicht, welche aus einem Mittel nach Anspruch 4 und einem der Ansprüche 5 bis 9 besteht oder dieses enthält, geleitet wird, wobei dieGases, in particular exhaust gases, so that the gas stream to be treated is passed through a granulate layer which consists of or contains an agent according to Claim 4 and one of Claims 5 to 9, the
Reinigung im Temperaturbereich von 20 bis 400 °C, insbesondere 60 bis 250 °C, vorzugsweise 120 bis 210 °C, durchgeführt wird. Cleaning in the temperature range from 20 to 400 ° C, in particular 60 to 250 ° C, preferably 120 to 210 ° C, is carried out.
PCT/EP2000/000239 1999-01-14 2000-01-13 Gas purifying agent, its method of production and its use WO2000041796A1 (en)

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