Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J7/00—Arrangement of devices for supplying chemicals to fire
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
  • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
  • F23G5/50—Control or safety arrangements
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
  • F23G2207/00—Control
  • F23G2207/30—Oxidant supply
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
  • F23G2207/00—Control
  • F23G2207/60—Additives supply
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J2217/00—Intercepting solids
  • F23J2217/20—Intercepting solids by baffles
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J2219/00—Treatment devices
  • F23J2219/10—Catalytic reduction devices
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J2219/00—Treatment devices
  • F23J2219/20—Non-catalytic reduction devices

Definitions

• the present invention relates to an incineration device with integrated heat recovery and flue gas purification and particularly to an incineration device for the incineration of waste, such as domestic and industrial waste.
• the invention further relates to the use of such a device for the incineration or thermal treatment - like gasification, pyrolysis or drying - of waste and waste products of the residual fraction of alternative processing techniques for the processing of waste, biomass and also contaminated combustibles of industrial, agricultural or fossil origin.
• These combustibles can be denoted by the collective name 'contaminated combustibles' or 'secondary combustibles'.
• the most important contaminants present in the flue gasses of incineration installations for incinerating contaminated combustibles - like waste, biomass, residual products or carbons with a high sulphur content - are carbon monoxide, unburned hydrocarbons, sulphur oxides (SOx), hydrochloric acid (HCI) and other haloid acids (HF, HBr), nitrogen oxides (NOx), heavy metals (dust), polychlorobiphenyls (PCB's), polychlorodibenzodioxins (PCDD's), polychlorodibenzofurans (PCDF's) and other halogenated aromatic and aliphatic hydrocarbons.
• the purification of flue gasses, combustion gasses and/or gasses of the thermal treatment of contaminated combustibles usually requires the following main steps: a. Limitation of the emission of carbon monoxide and unburned hydrocarbons; b. Dedusting and removal or neutralisation of heavy metals; c. Removal of nitrogen oxides; d. Desulphurization and removal of haloid acids; e. Removal of dioxins and other organic trace elements.
• US-A-5.501.161 describes a process for the thermal treatment of dusty and/or finely divided solids, which occur in the purification of flue gasses.
• the thermal treatment can serve to destroy halogenated, especially aromatic hydrocarbons and to remove ammonia and/or other volatile substances.
• the solids are supplied along a pre-set route to a filter device by means of a gas stream, the gas having at least the temperature of the thermal treatment.
• the solids can be subjected to a thermal post-treatment after filtration.
• EP-A-0.5.501.161 describes a device for the production of a homogeneously divided and directed stream of flue gas, whereby the vertical stream of gas is bent off by the terminal walls in a plural drain tank and by a cascade of two or more blades (S1 , S2, ...Sn) to separate the dust from the flue gas.
• the blades are positioned and dimensioned in such a way that the stream path of the flue gasses makes sharp bends. This sudden change in stream direction allows the deposition of the ash, which is entrained along with the flue gasses, in the lower part of the kettle house.
• Flue gasses usually contain large amounts of nitrogen oxides (NO x ), especially nitrogen monoxide (NO), which oxides are formed in the air upon incineration of waste or fossil fuel.
• NO x nitrogen oxides
• NO nitrogen monoxide
• the greenhouse effect is partially caused by N 2 O, which indeed is present in a much lower amount than CO 2 , yet its effect per molecule N 2 O over a period of 100 years is 290 times as high. NOx also contributes to the production of ozone, which is an important greenhouse gas, in the lower troposphere.
• NOx can form ozone in the lower troposphere, thereby contributing to the greenhouse effect and the formation of photochemical smog. NOx can also react with ozone in the higher troposphere/stratosphere, thereby contributing to the exhaustion of the protecting ozone layer. NOx is responsible in a direct and indirect way for half of the exhaustion.
• the deposition c.q. the precipitation of acid chemicals, for example nitrates, nitrites, sulphates, sulphites on the surface of the earth, on the land or in the water, under the influence of rain, snow, fog, clouds and even of dry particles. These deposits acidify the soil and the water, harm the ecosystems, the soil, the plants and cause corrosion and erosion.
• acid chemicals for example nitrates, nitrites, sulphates, sulphites on the surface of the earth, on the land or in the water, under the influence of rain, snow, fog, clouds and even of dry particles.
• the SNCR-process is the thermal reaction, in which reducing chemicals are used to reduce NOx to nitrogen (gas) in the absence of a catalyst.
• the most frequently used embodiment consists of the injection of ammonia, urea or another ammonia forming substance into the incinerator or burner, at a temperature between approximately 700°C and 1100°C, depending on which reducing agent is used.
• ammonia, urea or another ammonia forming substance into the incinerator or burner, at a temperature between approximately 700°C and 1100°C, depending on which reducing agent is used.
• Through the radical reaction between NO* and NH 2 » N 2 and H 2 O are formed. See for example EP-A-0.079.171.
• a SNCR-installation of the DeNOx section typically consists of a storage module for the reagent, dosage modules and injection lances.
• the reagent is pumped from the storage module into the dosage modules.
• the reagent, the pressurised air and the injection water are dosed in function of the relevant parameters.
• Reagent, pressurised air and/or water are preferably injected into the flue gasses by means of injection lances, preferably into the first draught of the kettle.
• the same reducing agent is injected, although at a temperature range between approximately 150 and 700°C, depending on the composition of the flue gas.
• the ammonia forming substance typically is mixed with the waste gas in a reaction chamber, which is provided with suitable catalysts. Through the reaction of NH 3 on the catalyst surface, NO is converted into N 2 . Through the occurrence of the side reactions 3 and 4, the actual consumption of ammonia is usually somewhat higher than stoichiometrically. If the amount of SO 2 is high, ammonium hydrogen sulphate is formed by the cascading effect of the last three reactions. This compound can block and de-activate the catalyst at a temperature of 230-270°C (depending on the supplier and the specific process conditions). Therefore, the temperature always needs to be kept sufficiently high.
• a SCR-installation of the DeNOx section typically consists of a storage module for the reagent, a dosage module, injection lances or an injection grit, and a catalytic reactor.
• the furnace gasses need to be heated again to the desired temperature, for instance by means of a gas burner, steam battery, heat exchangers and the like. In occurring instances, the furnace gasses need to be cooled by means of heat exchangers, and the like.
• the reagent is pumped from the storage module into the dosage modules.
• the reagent, pressurised air and the injection water are dosed in function of the relevant parameters.
• Reagent, pressurised air, and/or water are preferably injected or sprayed into the furnace gasses.
• Injection of the reagent into the furnace gasses is preferably carried out by means of a plurality of sprinkler heads, followed by a static mixer in the flue duct or by means of a grit that is introduced into the flue duct.
• a SCR-installation is typically introduced after a flue gas purification and at least after a first dedusting of the flue gasses (for example in an electrofilter).
• absorbents adsorbents and/or absorbents
• absorbents adsorbents and/or absorbents
• Suitable and known absorbents are for instance lime, calcium hydroxide, sodium bicarbonate, zeolites and clay minerals.
• dioxins and related or similar compounds for example PCB's, PCDD's and PCDF's
• PCB's, PCDD's and PCDF's are already present in the domestic waste that is incinerated in the waste incineration devices, but also that they are destroyed during the incineration.
• new dioxins are formed, especially at a temperature range between 450-250°C.
• the formation of the dioxins is enhanced by a number of parameters, such as:
• the emission of dioxins, furans and similar compounds is prevented by contacting the flue gasses with an absorbent, namely active carbon, and/or with a catalyst (for the latter, see for example US-5.512.259).
• an absorbent namely active carbon
• a catalyst for the latter, see for example US-5.512.259
• the adsorption preferably occurs at lower temperatures (T ⁇ 150°C)
• the catalytic reaction preferably is carried out at temperatures between 150° and 500°C.
• the object of the present invention is to provide an incineration device with integrated heat recovery and flue gas purification, suitable for the incineration of contaminated combustibles, such as waste, for example domestic and industrial waste, whereby the incineration, the recovery of energy and at least the following purification steps:
• the incineration device of the invention hereto comprises at least the following sections:
• one or more sections for removing acids the said section or sections being integrated in the incinerator, incineration chamber and/or heat recovery section; one or more DeNOx sections integrated in the incinerator, incineration chamber, heat recovery section and/or other sections for flue gas purification ; a stepped dedusting section comprising one or more sections integrated in the incinerator, the incineration chamber, the heat recovery section and/or other sections for flue gas purification ; one or more sections for the removal of chlorinated hydrocarbons integrated in the incinerator, the incineration chamber, the heat recovery section and/or other sections for flue gas purification an adapted measuring and control section for controlling the different steps of flue gas purification and heat recovery, suitable for incinerating contaminated combustibles.
• the different sections of the integrated incineration device may operate separately or overlap with each other, whereby in one section a plurality of contaminants are treated or are simultaneously present.
• the different actions of the sections can be carried out in one single part of the device.
• the invention further comprises the use of an integrated incineration device, as herein described and defined, for the incineration of contaminated combustibles, such as waste, for example domestic and industrial waste.
• FIG. 1 shows a schematic perspective view to an embodiment of the device of the invention.
• the incinerator, heat recovery in the form of an integrated steam kettle, and also the different sections for flue gas purification are indicated.
• the present invention provides an incineration device, comprising an incinerator with integrated heat recovery, for example in the form of a steam kettle, a thermal oil kettle or a gas-gas heat exchanger, a therein completely or partially integrated flue gas purification device, which flue gas purification device comprises primary or secondary means for preventing the formation and emission of contaminants, whereby the capturing and the destruction of contaminants occurs in a stage as early as possible in the process of incineration/recovery of energy.
• an incineration device comprising an incinerator with integrated heat recovery, for example in the form of a steam kettle, a thermal oil kettle or a gas-gas heat exchanger, a therein completely or partially integrated flue gas purification device, which flue gas purification device comprises primary or secondary means for preventing the formation and emission of contaminants, whereby the capturing and the destruction of contaminants occurs in a stage as early as possible in the process of incineration/recovery of energy.
• 'primary means' means are understood that directly interfere with the incineration process.
• 'Secondary means' are means, which limit the re-formation of contaminants or catch and/or destroy formed contaminants.
• the flue gas purification is integrated as much as possible in the incinerator installation with integrated heat recovery (hereafter also referred to as "incinerator-kettle").
• This integration has led to an entire new concept for an incinerator-kettle device, by which a very low amount of contaminants in the flue gasses can be obtained.
• This integration allows the installation for flue gas purification, connected in series, to operate as a safety filter or "police filter", meaning that it operates as a second step which captures eventual emission peaks, such that no exceeding of emission occurs, even when process failures occur.
• the incineration chamber or incinerator which is used in the device of the invention, is usually of the conventional type.
• the incineration chamber or incinerator substantially consists of a carrier for the combustible, a space for the incineration of volatile substances and an after- incineration chamber.
• a grate incinerator, a fluid bed incinerator or a static incinerator is used as incinerator, without, however, excluding other types of incinerators known to a person skilled in the art.
• the after-incineration chamber is a space that is connected in series with the described incinerator or incineration chamber. This space serves, by the supply of additional incineration air or supporting combustible or not, for the complete incineration (oxidation) of the gasses coming from the thermal treatment, like gasification, pyrolysis or drying.
• the waste or the combustible is introduced onto the grate, into the fluid bed or into the static incinerator, respectively, by means of an adapted feeding mechanism.
• different processes occur, namely: the drying of the waste, degasification of the waste, gasification of the waste leading to the formation of volatile substances which flow to the empty incinerator space and after-incineration chamber, pyrolysis of the solid compounds and the incineration of the gasses.
• the composition of the flue gasses is strongly influenced by the control of the 'incineration process'.
• Parameters for example the amount of air that is conducted through the waste layer or the bed, the temperature in the waste layer or the fluid bed, and the speed of the air in the waste layer or through the fluid bed are contributing to the form and concentration of for instance heavy metals in the flue gasses, the composition of the fly ashes, the amount of NOx in the flue gasses, the potential for the dioxin formation of the fly ashes and the like.
• the formation of contaminants in flue gasses can be controlled by the addition of reagents in the waste.
• the invention also relates to other thermal processes - like gasification, pyrolysis, drying - by which the solid, pasty, liquid or gaseous - contaminated combustibles are converted to gasses considerably.
• Heat recovery section
• the heat recovery section which is used in the device of the invention, generally is of the conventional type and is completely or partially integrated in the incinerator or (after)-incineration chamber.
• the heat recovery section consists of a heat exchanging surface with fitting dimensions, which contacts the gasses from the thermal process, such that the available energy is transferred to another medium.
• a steam kettle a kettle on thermal oil or an organic fluid or a gas- gas heat exchanger is used, without, however, excluding other types of heat exchangers known to a person skilled in the art or otherwise.
• a typical embodiment comprises a steam kettle, whereby the incinerator and the after-incineration chamber are completely integrated in the kettle. Different sections can be discriminated in the kettle, depending on whether the kettle is defined from the gas side or the water side.
• this part for contaminated combustibles usually is carried out as an empty space ('draught') with walls, which are built up as a heat exchanging surface. This means that these walls, in case of a steam kettle, consist of tubes through which a mixture of water and steam flows.
• the convection part in which the heat transfer between the media of the flue gasses and water substantially is realised by means of convection.
• the temperatures are substantially lower in this part.
• the convection part usually comprises a collection of tubes, through which a mixture of water and stream flows.
• the walls are usually built up in the same way as in the radiation part of the kettle.
• vapour can be formed in the economiser at certain thermal loads of the kettle.
• the water coming from the economisers is collected in a drum or a similar means and flows from here to the different evaporators of the kettle.
• the water-vapour mixture of the evaporators also flows back to the drum.
• a facility is installed through which the vapour subsequently flows from the upper part section of the drum (or a similar means) to the overheaters.
• the overheater the saturated steam coming from the drum is heated in the overheater to a temperature above the saturation temperature.
• a characterising feature of the invention is that the incinerator and the (after)-incineration chamber preferably are part of the heat recovery section.
• the extent of integration is also determined by the caloric value of the contaminated combustible, whereby it needs to be understood that the heat recovery section is only partially or not at all integrated in the incinerator or the (after)-incineration chamber for a combustible with a low caloric value.
• Absorbents also comprise, as defined here before, adsorbents.
• the yield of the reaction is also dependent on the temperature. An optimal consumption of one or more absorbents is achieved when they can react with the acid components in the flue gasses in one or more temperature windows.
• the invention provides the injection of one or more absorbents into the after-incineration chamber, at a temperature which is preferably in the range between 900° and 1050°C.
• the reagent and the reaction products are removed from the flue gasses at a substantially lower temperature (T>100°C), such that a substantial temperature range is covered and a sufficient long contacting period between the reagents at different optimal temperatures is achieved.
• T>100°C substantially lower temperature
• the composition of the flue gasses in waste incineration installations is different as compared to installations that are burned with fossil fuels. Therefore, the use of absorbents at high temperature according to the invention in waste incineration is a substantial progress as compared to existing technologies.
• the reduction of emissions of SOx in the incineration device of the invention can be achieved by one or more of the following steps:
• aborbents for example unslaked lime, calciumhydroxide, sodium carbonate and/or lime stone, at high temperature, such that SOx and haloid compounds are captured in a stage as early a possible.
• the sulphate salts are captured together with the fly ashes;
• This injection can be considered as a second step, by which a high removal yield and a low consumption can be combined;
• absorbents for example clay minerals and natural and/or synthetic zeolites
• a device filled with one or more absorbents for example a static bed, moving bed or fluid bed reactor, in the flue gas stream.
• the formation of NOx during the incineration process can be limited by an adjusted temperature control and air management in such a way that a stepped incineration is achieved.
• these measures are part of the incinerator control of modern installations.
• a recirculation of flue gas can be provided in order to further prevent the formation of NOx.
• the concentration of NOx in the flue gasses of waste incineration installations can be limited to approximately 200-400 mg/Nm 3 (11% oxygen, dry).
• a DeNOx section in the incineration device.
• This section reduces the nitrogen oxides present in the flue gasses to nitrogen gas by the injection of a reducing agent, for example ammonia or a nitrogen containing organic compound such as urea, or unsaturated hydrocarbons.
• a reducing agent for example ammonia or a nitrogen containing organic compound such as urea, or unsaturated hydrocarbons.
• a two- stepped DeNOx installation is integrated in the incinerator-kettle part of the incineration device.
• the NOx is reduced in a first step starting from the initial value to a pre-set value by means of the SNCR principle. This occurs in the after-incineration chamber.
• a catalyst volume is provided at the exit of the steam kettle, preferably between the evaporator bindles and the economiser, the catalyst volume eventually being preceded by an additional injection of the reducing agent. NOx is further reduced to the pre-set emission value in this second step.
• the invention also comprises a combined injection of reducing agent with adsorbents and absorbents, for example lime and zeolite.
• reducing agent for example lime and zeolite.
• Such a combined injection has the following advantages: a higher reactivity of the reagent by a higher degree of molecular collisions (reducing agent in suspension of lime and zeolite), simplification of the device, simplified process control, enhanced efficiency (lower consumption of reagents).
• the reducing agent can be injected in the incineration chamber (SNCR location) or just before the catalyst; - the application of one or more SCR DeNOx catalysts in non-purified or partially purified flue gasses; the catalyst preferably is provided with a purification mechanism or is self-purifying;
• SNCR DeNOx installation comprising a combination of SNCR and SCR DeNOx, substantially as known from the state of the art.
• the SNCR DeNOx installation can operate with a high amount of ammonia sludge and with a high reduction yield, through which the necessary volume of the SCR DeNOx catalyst, connected in series with the SNCR DeNOx installation, is optimised;
• adsorbents for NO 2 for example clay minerals, natural zeolites, synthetic zeolites, Al 2 O 3 , SiO 2 , AI 2 O 3 - MgO, TiO 2 , SnO 2 and/or ZrO 2 at a suitable adsorption temperature, by which the NOx-compounds are destroyed in the furnace by the recirculation of the loaded adsorbent to the furnace;
• - oxidation of NO to NO 2 can for instance occur by means of a solid catalyst, comprising a monolithically structure, a solid catalyst applied on a part of the heat recovery section, a solid catalyst applied on a carrier material and/or a catalyst which is injected into the gasses as a powder or suspension.
• the formation of dust in the incinerator c.q. the incineration process or the thermal conversion process is limited by one or more of the following measures:
• grate control for example by using proportionally controlled valves.
• a SEGHERS® grate is used, whereby the horizontal (sliding) and vertical (fire hook) movement are controlled independent from each other, such that, with this grate, in contrast to with other commercially available grates, it is possible to control the movement of the burning waste layer in function of the incineration behaviour of the waste.
• the stirring of the waste can be controlled, as well with respect to speed as frequency - in function of the necessity to obtain a good incineration.
• a moving bed filter consisting of a (inert) filling which slowly falls down from the top to the bottom between two perforated walls. The filling and the captured dust are collected at the bottom of the filter, filtered, and again transported to the top.
• a filter comprising filter cloths and top-filters, preferably made of metal or a metal alloy.
• the dedusting preferably occurs in two steps: a first dedusting in the empty draughts (radiation part) of the kettle or before the transition between the empty draughts and the overheater bindles, followed by a final dedusting at the exit of the kettle, for example by means of a classical cloth filter.
• the first step is new and constitutes, especially in combination with the second step, a substantial improvement as compared to the state of the art.
• the second step as such is known and is for the moment used as such in the majority of HVI's.
• the emissions of PCDD, PCDF, PCB and other halogenated aromatic or aliphatic hydrocarbons are reduced by one or more of the following steps:
• the condensation preferably takes place at higher temperature by providing suitable contact compounds or wherein the heavy metals are de-activated at a suitable temperature with nitrogen or sulphur containing inhibitors;
• dioxins such as the injection of lime in an after-incineration chamber
• these compounds concentrate dioxins and/or precursors thereof on the surface of the injected absorbents or absorb one or more dioxin building blocks, such as chlorine;
• features are provided, which prevent or limit the re-formation of PCDD, PCDF, PCB and similar compounds. These features comprise one or more of the following embodiments:
• the catalyst is now positioned in less purified flue gasses, as a consequence of which features are required with which for example the deposition of salts on the catalyst surface, poisoning of the catalyst by alkali metals and sulphur and deposition of dust may be avoided or the consequences thereof be compensated.
• These features include according to the invention, one or more of the following steps:
• pollutants are only measured in the fireplace, possibly a limited number of compounds is measured before or after one of the flue gas purification steps (e.g. oxygen at the exit of the kettle, HCI before the half wet reactor, dust after the sleeve filter , etc.).
• one of the flue gas purification steps e.g. oxygen at the exit of the kettle, HCI before the half wet reactor, dust after the sleeve filter , etc.
• An essential part of the present invention consists of implementing different measuring principles and control theories. Therewith, parameters such as usability at high temperature, interference of dust or other chemical components, possibility of measuring values in one plane in stead of a point, have been evaluated. Also the most suitable control philosophy has been determined.
• a measuring and control section which comprises one or more of the steps described hereafter:
• FIG 1 an embodiment of an incinerating device of this invention is shown, in which the incinerator with after-incineration chamber (which may also be part of the first draught or of the radiation part of the recuperation kettle), the recuperation kettle consisting of a radiation part and convection part, as well as the various sections for the purification of the flue gasses are indicated with a few of the corresponding preferred temperature profiles.
• the incinerator with after-incineration chamber which may also be part of the first draught or of the radiation part of the recuperation kettle
• the recuperation kettle consisting of a radiation part and convection part, as well as the various sections for the purification of the flue gasses are indicated with a few of the corresponding preferred temperature profiles.
• the flue gas stream flows subsequently through a desulphurisation section (DeSOx) and neutralisation of hydrogen-halogen compounds, a section for the removal of nitrogen oxides (DeNOx), a section for dedusting and removal of heavy metals (DeDust) and a section for removing dioxins and compounds related thereto (DeDiox).
• DeSOx desulphurisation section
• DeNOx nitrogen oxides
• DeDust heavy metals
• DeDiox dioxins and compounds related thereto
• the formation of CO and unburned hydrocarbons (CxHy) is limited to a minimum by controlling the gasification - incineration process, as described above. It will be clear to the man skilled in the art that the sequence of the purification steps may be changed and that a modification of the optimum temperature profiles should be taken into account.

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• Engineering & Computer Science (AREA)
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• Treating Waste Gases (AREA)
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• Cleaning By Liquid Or Steam (AREA)
• Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)

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• 2002
  • 2002-06-27 ES ES02754776T patent/ES2305274T3/es not_active Expired - Lifetime
  • 2002-06-27 WO PCT/EP2002/007119 patent/WO2003002912A1/en active IP Right Grant
  • 2002-06-27 AT AT02754776T patent/ATE392590T1/de active
  • 2002-06-27 EP EP02754776A patent/EP1399695B1/de not_active Expired - Lifetime
  • 2002-06-27 CN CN02816008.8A patent/CN1266416C/zh not_active Expired - Lifetime
  • 2002-06-27 DE DE60226137T patent/DE60226137T2/de not_active Expired - Lifetime

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