• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a process for the inertization of heavy metals, such as e.g. hexavalent chromium, chlorides and other salt formers as well as soluble solids and metallic contaminants in ashes and / or wastes from incineration processes or other thermal, chemical, mechanical processes. It is primarily characterized in that the combustion or the thermal, chemical, mechanical process is followed by a calcination. As a result, it is possible to remove excess water as well as to inertise / stabilize or fix heavy metals, chlorides and other salt formers as well as soluble solids and metallic contaminants.
    公开号:AT512739A1
    申请号:T445/2012
    申请日:2012-04-13
    公开日:2013-10-15
    发明作者:Gerald Dipl Ing Fraissler；Kurt Dipl Ing Kaufmann；Sebastian Dipl Ing Dr Kaiser；Guenter Dipl Ing Jaritz
    申请人:Andritz Energy & Environment Gmbh；
    IPC主号:
    专利说明:

    ··· »♦ · · · · · · · · ··························································· · · Φ · ·
    The invention relates to a process for the inertization of heavy metals, such as e.g. hexavalent chromium, chlorides and other salt formers, as well as soluble solids and metallic contaminants in ashes and / or waste from incineration processes or other thermal, chemical, mechanical processes.
    Slags, flyashes, dusts and reaction products from incineration, especially of refuse derived fuel (EBS) burning fluidized bed boilers have high pollutant contents. Of course, other waste materials from thermal, chemical, mechanical processes such as e.g. Sludges, slags, dross, dusts from the metal industry, the metallurgical industry, chemical industry or other industries are treated. Depending on the legal requirements, their current disposal with respect to top and / or underground storage is often very costly for plant operators.
    A major problem in landfilling is the formation of heavy metals, chlorides and other salt formers, as well as metallic contaminants and other readily dissolvable materials. These can end up in the landfill and, through the presence of suitable reactants and conditions, can promote further toxic compounds and contaminants.
    DE 693 01 367 T2 (EP 0 566 376 B1) discloses a method for sintering fly ash from burnt household waste. Carbon is added here in the form of pure coal dust. For sintering also high temperatures of over 900 ° C are required, which means a high energy consumption.
    The aim of the invention is therefore a recovery process for the inertization of heavy metals such as e.g. hexavalent chromium, chlorides and other salt formers as well as soluble solids and metallic contaminants in ashes and / or wastes from incineration processes or other thermal, chemical or mechanical processes. This method should also work from an economic point of view (investment, operating, disposal costs in terms of transport and landfill).
    The invention is therefore characterized in that the combustion or the thermal, chemical, mechanical process is followed by a calcination. Depending on the moisture content and alkalinity / basicity of the waste, calcination now achieves stabilization of the heavy metals, inerting and the like. of hexavalent chromium, stabilization of chlorides and other salt formers as well as soluble solids and metallic contaminants. At high moisture content of abandoned waste, existing water should be separated to achieve a weight reduction to reduce disposal costs (transport, landfill).
    A favorable embodiment of the invention is characterized in that for the calcination warm flue gas / exhaust gas with the highest possible carbon dioxide content is used as the heating medium, the gas temperature between 200 and 500 ° C is 1
    7243-C AT * · · · * * * Μ M M M M M M M M M M M M M ft ft ft ft ft ft ft ft It is favorable if the calcination is preceded by a wet-chemical treatment. In some cases it has proven to be advantageous if the calcination is preceded by a preparation, for example granulation, which follows a possible wet-chemical treatment or directly to the Combustion or the thermal / chemical or mechanical process can connect. In the case of upstream granulation, the granulate form and strength should be optimized to the thermal reactor provided for the calcining step. The mechanical stress during the calcining step should be kept as low as possible on the granules applied, in order to avoid abrasion and breakage and, as a consequence, dust accumulation, since this has negative effects on storage, transport and disposal.
    The invention will now be described by way of example with reference to the drawings, in which FIG. 1 is a flow chart of the method according to the invention,
    2 shows a possible system diagram of the method according to the invention in a combustion plant,
    3 shows a variant of method steps according to the method according to the invention.
    1 schematically shows the method according to the invention, starting from an incinerator / thermal, chemical, mechanical process, the ash / waste accumulating there with heavy metals, chlorides and other salt formers as well as soluble solids and metallic contaminants o.ä. is charged, a calcination is zugefuhrt. Of course, other waste materials from thermal, chemical, mechanical processes such as e.g. Slag, slag, dross, dusts from the metal industry and the metallurgical industry, chemical industry or other industries are treated. If flue gas / offgas with a high carbon dioxide content is used for calcination, the solubility of existing metal contaminants, which have amphoteric character, can be reduced to carbonates by adapting the basicity by reaction of alkalinity / alkalinity-determining metal hydroxides with carbon dioxide contained in the flue gas. The degree of carbonation is oriented accordingly to the optimum of the lowest solubilities in terms of disposal, with the lowest solubilities being found in the pH range from 8.0 to 12. At the same time, carbonation of chlorides and other salt formants as well as other soluble solids stabilize according to the ion displacement principle. In addition, excess water is separated in order to reduce weight and, associated therewith, also reduce the disposal costs
    7243-C AT, and this may be added water even in a prone upstream process step.
    High basicity wastes / alkalies of pH> 11 and presence of aluminosilicate-rich phases lead to their activation in the form of hydrate gels which are used for crosslinking (geopolymerization / condensation) involving heavy metals, chlorides and other salt formers as well as soluble After lowering the alkalinity / basicity, solids can lead to pH values <11 and cause the fixation of further metallic contaminations by inclusion in the solid binder matrix formed by crystallization and crosslinking. Geopolymers are characterized by a high thermal and chemical resistance under acidic conditions, whereby the above-mentioned contamination can be permanently stabilized / fixed.
    2 shows a simplified system diagram for carrying out a variant of the method according to the invention with reference to an incinerator.
    The incineration plant is shown here as a circulating fluidized bed boiler 1 with cyclone 2, afterburner chamber 3 and dust collectors 4 including multicyclone 5. The untreated fly ash 6 is supplied via a buffer tank 7 in a mixer / kneader 8 a wet chemical treatment. With the addition of water 9 and other alkaline reactants as described here e.g. Bases 10 and / or nitrate 11 is here the wet-chemical treatment. Due to the hydration / oxidation of the metallic aluminum or other base metallic phases, hydrogen / ammonia is released depending on their content in the fly ash. Accordingly, the formation of an explosive atmosphere in the mixer / kneader 8 and in its immediate vicinity by gas purging must be prevented. The fuel gas contained in the exhaust gas is recycled to the energy use in the combustion chamber 1. An upstream scrubber 20 is used for the separation of the valuable ammonia, which can be used for denitrification in the combustion process or recycled.
    After completion of the mechanical stress in the mixer / kneader 8 and discharge there is a risk that upon further handling the moist thixotropic mixture by crystallization and / or polymerization / condensation due to existing binder phases within a short time uncontrolled sets and forms a solid mass. The aim of a susceptible subsequent Stückigmachung / granulation is therefore in terms of requirements, storage and transport technology optimal shape and dimensional stability and to achieve optimum granule shape and strength for the downstream Kalzinierschritt. After the mixer / kneader 8, the product 13 can be conducted from the wet-chemical treatment in a granulator 14 for mixing and shaping. 3
    7243-C AT ♦ * • φ
    In addition, binder 15 is introduced into this granulator 14 to stabilize the granules in terms of shape and strength. With a correspondingly high alkalinity after the wet-chemical treatment, the addition of fine bed ash with a high aluminosilicate content and a high specific surface area is sufficient since it is activated to form hydrate gels and crosslinked. In addition, fine bed ash has high proportions of hydraulically acting phases. In any case, in downstream calcination additives that lead to the formation of geopolymers, due to their good thermal and chemical resistance to use under acidic conditions.
    Fine bed ash from the combustion process also has the advantage that its problematic contents, e.g. Chlorides and other salt formers, heavy metals, soluble solids, are negligibly small.
    By optimizing the shape and / or dimensional stability in terms of storage and warehousing, it is possible to ensure that the product from the wet-chemical treatment does not uncontrollably set due to existing binder phases and form a solid mass, but can still be conveyed, stored and transported.
    The product 16 from the granulation step is fed to a calciner 17. This can be, for example, a multi-level oven, whereby the process parameters temperature and dwell time can be varied per oven (floor). The deck oven also offers good circulation and flow through the bed and consequently the desired contact with the furnace atmosphere. The mechanical stress during the calcining step is to be kept as low as possible on the product in order to avoid abrasion and breakage of a dust, since this can have negative effects on storage, promotion and disposal.
    The heating of the calcination furnace 17 is here convection with flue gas 18 in countercurrent. However, this can also be used in combination with other types of drying, e.g. Radiation drying and contact drying happen. The invention is not limited to the use of a multiple-hearth furnace, but equivalent thermoreactors with corresponding properties may also be used, e.g. Drum dryer, belt dryer, etc. The flue gas composition is important for the provision of carbon dioxide for carbonation and subsequently for the lowering of alkalinity / basicity. The provision of required carbon dioxide may additionally be accomplished by addition of suitable waste / ash additives which thermally decompose during the calcination step, for example, urea, carbonates, and the like.
    The exhaust gas 19 is returned to the heat recovery in the combustion chamber 1, which leads to energy use. 4
    7243-CAT
    • * * · · · • * ♦ · · · · · · · · * #
    Fig. 3 shows the process step calcination, which is followed by the combustion or a thermal, chemical, mechanical process.
    The recycling process according to the invention is downstream of the combustion process / thermal, chemical, mechanical process and can be connected or independent
    Plant operated. This can be the combustion or the thermal process without
    Intermediate step be followed, if the ash has no base metal phases. Otherwise, wet-chemical treatment may be used in combination with granulation.
    The thermoreactor 17 used is gas-tight and a negative pressure is produced by means of a suction train. The mode of operation preferably takes place according to the continuous or quasi-continuous principle and makes it possible to selectively influence the product quality with regard to landfilling variable residence times. Due to the design of the thermoreactor 17, the waste / ash 16 to be treated should be flowed through well by the flue gas / exhaust gas 18 in order to allow the desired contact with the flue gas / exhaust gas. If granules are introduced into the thermoreactor 17, abrasion and breakage thereof and, as a consequence, dust accumulation are to be avoided by the selected aggregate, since this has negative effects on storage, conveying and disposal. Here, as far as possible, a form-retaining procedure should be chosen. From the combustion process / thermal process branched flue gas / exhaust gas 18 with a high carbon dioxide content is particularly useful for its reuse as a heating medium. For connected and independent systems, burners or combustion reactors can also be used to generate flue gas. The gas temperature at the inlet of the thermoreactor should be between 200 and 500 ° C. The exhaust gas 19 at the outlet can be fed back to the combustion process as recirculation gas.
    The invention is not limited by the drawings and description. Thus, a number of different thermoreactors, such as u.a. Deck ovens, but also, for example, drum dryer, belt dryer or similar. be used. 5
    7243-C AT
    权利要求:
    Claims (6)
    [1]
    Claims 1. Method for inerting heavy metals, such as e.g. hexavalent chromium, chlorides and other salt formers as well as soluble solids and metallic contaminants in ashes and / or wastes from incineration processes or other thermal, chemical, mechanical processes, characterized in that the combustion or thermal, chemical, mechanical process is followed by a calcination,
    [2]
    2. The method according to any one of claims 1, characterized in that for the calcination warm flue gas is used with the highest possible carbon dioxide content as the heating medium, wherein the gas temperature is between 200 and 500 ° C.
    [3]
    3. The method according to claim 1 or 2, characterized in that by adding suitable additives to the waste / ash, which decompose thermally during the calcining step, for example, urea, carbonates, or the like. and carbon dioxide is released.
    [4]
    Process according to any one of Claims 1 to 3, characterized in that the degree of carbonation in the product of calcination is at the optimum of the lowest solubilities of the heavy metal contaminants, e.g. hexavalent chromium, chlorides and other salt formers, as well as soluble solids and other metallic contaminants, with alkalinity / basicity preferably in the pH range 8 to 12.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that the calcination is preceded by a wet chemical treatment.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the calcination is a piece preparation, for example, granulation, upstream. 6,7243-C AT
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    同族专利:
    公开号 | 公开日
    EP2650391B1|2018-02-14|
    PL2650391T3|2018-08-31|
    EP2650391A1|2013-10-16|
    AT512739B1|2014-04-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPH10151437A|1996-09-26|1998-06-09|Toru Kubota|Treatment of heavy metal and dioxin in incineration ash at low temperature|
    WO2000028094A1|1998-11-05|2000-05-18|Paul Wurth S.A.|Method for the heat treatment of residues containing heavy metals|
    EP1918031A1|2006-10-30|2008-05-07|ASH DEC Umwelt AG|Method of detoxification and utilization of fly ash|
    DE3815632C2|1988-05-07|1991-08-08|Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe, De|
    EP0566376B1|1992-04-15|1996-01-24|Kabushiki Kaisha Kobe Seiko Sho|A method and equipment for sintering fly ashes of incinerated municipal waste|
    US6120577A|1998-03-25|2000-09-19|Ltv Steel Company, Inc.|Treatment of steel mill waste metal oxides|
    FR2801521B1|1999-11-29|2002-04-26|Commissariat Energie Atomique|PROCESS AND DEVICE FOR TREATING AND CONDITIONING AN EFFLUENT FOR VITRIFICATION|
    AT409350B|2000-06-28|2002-07-25|Kostjak Michael Dipl Ing Dr Te|METHOD FOR DETACHING METALLIC ALUMINUM FROM ALUMINUM-CONTAINING SOLID WASTE|CN108202077A|2018-01-02|2018-06-26|上海炼升化工股份有限公司|A kind of recycling processing method of equilibrium catalyst for catalytic cracking process|
    CN112808740A|2020-12-30|2021-05-18|格润过程科技有限责任公司|Method for treating chromium slag by using plant extract|
    法律状态:
    2015-09-15| PC| Change of the owner|Owner name: ANDRITZ AG, AT Effective date: 20150721 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA445/2012A|AT512739B1|2012-04-13|2012-04-13|Process for the inertization of heavy metals, e.g. hexavalent chromium, chlorides and other salt formers as well as soluble solids and metallic contaminants|ATA445/2012A| AT512739B1|2012-04-13|2012-04-13|Process for the inertization of heavy metals, e.g. hexavalent chromium, chlorides and other salt formers as well as soluble solids and metallic contaminants|
    EP13001753.6A| EP2650391B1|2012-04-13|2013-04-05|Method for the inertisation of heavy metals such as hexavalent chromium, chlorides and other salt-forming compounds and soluble solids and metallic contaminations|
    PL13001753T| PL2650391T3|2012-04-13|2013-04-05|Method for the inertisation of heavy metals such as hexavalent chromium, chlorides and other salt-forming compounds and soluble solids and metallic contaminations|
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