CN101874180B - Flameless thermal oxidation apparatus and methods - Google Patents
Flameless thermal oxidation apparatus and methods Download PDFInfo
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- CN101874180B CN101874180B CN2008801186797A CN200880118679A CN101874180B CN 101874180 B CN101874180 B CN 101874180B CN 2008801186797 A CN2008801186797 A CN 2008801186797A CN 200880118679 A CN200880118679 A CN 200880118679A CN 101874180 B CN101874180 B CN 101874180B
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Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
- F23G7/065—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
- F23G7/066—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel preheating the waste gas by the heat of the combustion, e.g. recuperation type incinerator
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C2900/00—Special features of, or arrangements for combustion apparatus using fluid fuels or solid fuels suspended in air; Combustion processes therefor
- F23C2900/99001—Cold flame combustion or flameless oxidation processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Incineration Of Waste (AREA)
- Tunnel Furnaces (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A thermal oxidizer is provided in which off-gases in a process stream are thermally oxidized within substantially the entire interior volume of an oxidation chamber. The thermal oxidation is conducted without the presence of a flame or with only a minor portion of one or more fuels being combusted in a flame.
Description
Background of invention
The present invention generally relates to the thermal oxidizer of the organic compound that is used for the oxidation process stream, and relates more specifically to move the apparatus and method that the thermal oxidizer of this use Flameless thermal oxidation comes decomposing organic compounds.
These thermal oxidizers are often used in process stream and are discharged into and make it stand high temperature before the atmosphere and one or more gases or steam in the oxidation process stream.Gas in the process stream typically refers to waste gas and generally includes VOC (VOC), half volatile organic compound (SVOC) and/or hazardous air pollutants (HAP).The process stream that comprises waste gas is the byproduct of industry, manufacturing industry or power generation process normally.
In conventional thermal oxidizer, through process stream is combined with the oxygen containing air-flow of bag, and then the fluid stream that combines is passed the flame that produces through the fuels sources of burning such as natural gas or burning gases and off-gas oxidizing is formed carbon dioxide and water.Like this, but thermal oxidizer converts the organic compound of contaminated environment the innoxious compound of safety dumping to atmosphere to.
But use flame to make compound thermal decomposition in thermal oxidizer can cause the nonconforming air pollutants of generation such as NOx and CO usually.NOx is owing to localized high temperature regions forms, and CO is the unburnt product of contingent flue gas during the thermal oxidizer combustion process.
In the NOx that in the thermal decomposition process that reduces compound, produces and the effort of CO content, the no flame oxidation technology of known use thermal oxidizer.United States Patent (USP) the 5th, 165 has disclosed the instance of a this no flame oxidation technology in No. 884.In this patent, the mixture of gas or steam and air and/or oxygen flows in the bed matrix of solid heat proof material, and this matrix has been preheating to the above temperature of autoignition temperature of mixture.This mixture is lighted in bed substrate and exothermic heat of reaction continues the reaction ripple to form in the bed substrate certainly.This process is used for making the generation of NOx, CO and unburnt other product during process stream being discharged into atmosphere to eliminate process stream specific gas or steam before minimum.Allegedly use said method can obtain per 1,000,000 BTU less than the NOx of 0.007lb (as NO
2) the discharge capacity and the CO amount that is lower than 10ppm of hot NOx.
The favourable aspect of the bed substrate in No. the 5th, 165,884, the above-mentioned United States Patent (USP) is in combustion process its fixing and stopping reaction ripple.But the bed matrix occupies the major part of process reactor internal capacity, reduces thus to can be used for the open volume that process stream flows.Therefore the reducing to shorten at commercial production flow of liquid given through amount down for the residence time capable of using of given reactor size of open volume in the reactor shorten the time capable of using of elimination harmful waste.In addition, bed substrate forms remarkable pressure drop, and this has increased the operating cost of process, and reason is that process stream is getting into the pressure that must stand to increase before the process reactor.This pressure drop often increases in time because from the particle matter of process stream accumulate in the bed substrate or the bed material owing to thermal shock is degraded.Finally, the increase of the pressure drop of leap bed substrate possibly require to change a bed material.
Therefore need a kind of like this thermal oxidizer, it produces minor N Ox and CO and does not have above-mentioned shortcoming.
Summary of the invention
The present invention provides a kind of method that is used for each composition of Flameless thermal oxidation in having the oxidizing chamber of interior lining, said method comprising the steps of: at first heat said oxidizing chamber lining; And under the condition of the thermal oxide that starts said composition owing to heat transmission, said composition is transported to said oxidizing chamber then from said heated oxidizing chamber lining.At first the step of heated oxide chamber lining comprises lining is heated to the pre-selected temperature, and this temperature is enough to radiation or otherwise transmits the thermal oxide that enough heats start each composition in the fluid stream.After refractory liner is heated to the pre-selected temperature, can comprise that each composition of one or more fuel is transported to oxidizing chamber in fluid stream.Condition in the control fluid stream is to produce the Flameless thermal oxidation of each composition in the fluid stream that is caused by the heat transmission from refractory liner.Therefore to start and to keep Flameless thermal oxidation and do not need bed substrate, need not does not have the needed pre-heating fuel stream of flame oxidation process and/or combustion air flow or flue gas recirculation like routine from the heat transmission of refractory liner in this method dependence.
The present invention also provides a kind of method that in the oxidizing chamber with internal refractory lining Flameless thermal oxidation comprises each composition of fluid stream of one or more fuel that is used for; Said method comprising the steps of: but fluid stream and the combustion air that comprises the thermal oxide composition is provided, but said thermal oxide composition comprises one or more fuel; In said oxidizing chamber, said refractory liner is heated to the pre-selected temperature; And then owing to from the heat transmission of said refractory liner and the said composition of thermal oxide does not have to make said fluid stream pass said oxidizing chamber under the condition of recirculation of said fluid stream.
At an embodiment, one or more propellant compositions are burnt so that refractory liner at first is heated to preselected temperature with the visible flame mode in the fluid stream.In start-up mode, the total concentration of propellant composition can be in combustible range in the fluid stream.Perhaps, the total concentration of propellant composition outside combustible range, but through the combustion air that exists in propellant composition and the fluid stream incomplete the mixing produce flammable mixture, thereby produce diffusion or the partly-premixed flame that closes.During carrying out the transition to the Flameless thermal oxidation pattern; In burner, burn with the external mixture that prevents such as moving on to combustible range with mixing of combustion air with local concentration with the visible flame mode with propellant composition through enhancement fuel, thus the flame in the quenching fluid stream.Also can use local concentration to change to other method beyond the combustible range with propellant composition.
VOC, half volatile organic compound and/or hazardous air pollutants can be used as the additional composition in the fluid stream and exist and during the Flameless thermal oxidation pattern by thermal oxide.These additional compositions are derived from from the process stream of industry, manufacturing industry or power generation process usually and must before process stream being discharged into atmosphere, remove.This process stream can be supplied with some in the needed combustion air in this process, all or a kind of also not have.
If desired, can increase additional heat to oxidizing chamber offsets through the heat loss of oxidizing chamber shell or the cooling effect of fluid stream.Can be through such as increasing continuously additional heat with visible flame mode one or more fuel in another fluid of oxidizing chamber internal combustion stream.Alternatively, can be through such as periodically increasing additional heat off and on initial heating mode operation thermal oxidizer.
When process of the present invention is moved in no flame oxidation pattern, realized less than the 5ppm dry weight, less than the 2ppm dry weight and even less than the NOx content of 1ppm dry weight, and less than the CO content of 1ppm dry weight.Employed NOx of this paper and CO content are expressed as the content based on per 1,000,000 volumes of dry weight.Even when oxidizing chamber increases additional heat, NOx content and the CO content that is lower than the 1ppm dry weight between 1 to the 12ppm dry weight have also been realized.
Description of drawings
Accompanying drawing forms this specification part and will combine accompanying drawing to read, and wherein identical Reference numeral is used to represent identical parts among each figure:
Fig. 1 is the vertical view of thermal oxidizer according to an embodiment of the invention, and the each several part of thermal oxidizer is broken away so that each details of structure to be shown; And
Fig. 2 is the enlarged side view of the burner part of thermal oxidizer along the vertical section intercepting, and some part schematically is shown.
The specific embodiment
Existing turn to Fig. 1 at first in more detail, an embodiment of thermal oxidizer who is used for the Flameless thermal oxidation of each composition of fluid stream always representes with Reference numeral 10.Fluid stream is by arrow 11 expressions, and normally with continuous or intermittent mode gas or the steam flow in thermal oxidizer 10 internal flows.Oxidable composition in the fluid stream 11 can be the form of gas, liquid and/or solia particle.The instance of these compositions comprises fuel, waste products, organic compound (comprising VOC and half volatile organic compound) and/or hazardous air pollutants.
There are the shell 14 interior interior zones of lining to limit open interior volume 18, Flameless thermal oxidation take place, as described in more accomplishing like hereinafter in this volume 18.The size of open interior volume 18 do be paired in the special process that will carry out use, for the fluid stream 11 that flows through thermal oxidizer 12 with the volumetric flow rate that is designed, can obtain desired residence time.Usually, this residence time is chosen to realize completing combustion and/or desired elimination removal efficient for the oxidable composition in the process stream.
As can know from Fig. 2 find out, in the embodiment shown, burner 24 comprises external shell 32, this external shell 32 is lined with the refractory liner 34 of one or more layers aforementioned type.Insulating lining 35 can be arranged between the inner surface of hot side refractory liner 34 and external shell 32.Housing 32 is preferably columnar, but can have the cross section of polygon or other structure.This housing 32 has sidewall 36 and corresponding upstream extremity 38 and downstream 40 relatively.There is the housing 32 of lining to limit open inside cup 42, this inside cup 42 and oxidizing chamber 12 fluid flow communications that are arranged on burner 24 downstream.The downstream 40 that the chokes portion 44 of being processed by refractory material can be arranged on burner shell 32 is sentenced to be provided from cup 42 passage 45 of the reduced of oxidizing chamber 12 downstream.Chokes portion 44 can have square-section as shown in the figure or it can be formed with intilted entrance and exit end to form the more structure of aerodynamic.In some applications, can omit chokes portion 44.
Nozzle assembly 46 is arranged on upstream extremity 38 places of burner shell 32, so that ignitable fuel and air mixture are transported to cup 42.In one embodiment, nozzle assembly 46 comprises fuel gun 48 elongated, centralized positioning, fuels from 50 pairs of these fuel guns 48 of fuels sources through pipeline 52.The volume flow rate that suitable flow regulator 54 is regulated the fuel that leads to fuel gun 48.Fuel gun 48 ends at fuel end 56, and this end has the aperture (not shown), and the fuel stream that is indicated by arrow 57 is discharged in the cup 42 through these apertures.Fuel gun 48 can be axially-moveable, thus the location of fuel terminal 56 can with respect to around Adam's apple structure 58 and change, this Adam's apple structure has the cross section and reduces the zone, as hereinafter more fully as described in.Alternatively, the second fuel end related with fuel gun 48 or other fuel gun (not shown) can be from terminal 56 translations of first fuel, thereby fuel can spray at the diverse location with respect to Adam's apple structure 58.
Fuel gun 48 is centered on by tank body 59, wherein has a plurality of volution blades 60 to be arranged in the annular opening of tank body 59 extension on every side.Each volution blade 60 is installed to isolated ring 63a and 63b, and ring 63a and 63b and annular opening adjacent fixed are to tank body 59.The internal diameter of the ring 63a that is provided with near fuel terminal 56 roughly equates with the internal diameter of tank body 59, thereby it can not hinder fluid mobile along towards the direction of fuel end 56 tank body 59 in.The internal diameter of another ring 63b is less than the internal diameter of tank body 59, thereby it is used to hinder fluid mobile along away from the direction of fuel terminal 56 tank body 59 in.The combustion air flow that comprises oxygen that arrow 61 indicates or other oxidant flow through volution blade 60 entering tank bodies 59 and get into subsequently in the cup 42.Volution blade 60 is given burning gases stream with strong rotatablely moving, thereby the auxiliary combustion air mixes with fuel from terminal 56 dischargings of fuel flows.Combustion air supplies to tank body 59 through pipeline 62 from combustion air source 64, and comes the adjusted volume flow rate through flow regulator 65.Also can use other mechanism to give desired mix of fuel stream 57 with burning gases stream 61.As only instance of these mechanisms, with the one or more inclination discharge nozzles that rotatablely move burning gases stream 61 is transported in the tank body 59 through giving combustion air.Sufficient turbulent flow can otherwise be formed so that fuel stream 57 and combustion air flow 61 intimate admixture just not necessarily will be given fuel stream 57 or combustion air flow 61 with vortex movement as long as should be appreciated that.
Can at ambient temperature combustion air flow 61 and/or fuel stream 57 be supplied to burner 24.Perhaps, can supply with heat through the combustion process of generation in thermal oxidizer 10 or from other suitable thermal source in this heat exchanger through heat exchanger 66 preheated burning air stream 61 and/or fuel stream 57.The pressure feed that combustion air flow 61 and fuel stream 57 preferably do not have to reflux to be enough to force fluid stream 11 to flow through oxidizing chamber 12 forward is to burner 24.
The source 64 of combustion air flow 61 can comprise the part of process stream 68 or all, this process stream comprises waste products, organic compound (comprising VOC and half volatile organic compound) and/or hazardous air pollutants.The instance of these compounds and pollutant comprises hydrocarbon, sulfur-containing compound, chlorinated solvents, halogenated hydrocarbons liquid, dioxin and Polychlorinated biphenyls.Therefore process stream 68 can be the byproduct of waste gas or industry, manufacturing industry or power generation process.According to the special properties and the oxygen content of process stream 68, combustion air flow source 64 also can comprise atmosphere or some additional oxygen source.In addition, the one or more part or all of combustion air capable of bypass pumping chamber 59 of process stream 68 also can be at one or more downstream positions such as being transported to cup 42 and/or oxidizing chamber 12 through injection tip 70,71 and/or 72. Injection tip 70,71 and 72 quantity and position can change to adapt to application-specific.Flow regulator 73a-c is arranged to allow regulate the flow rate of the each several part of process stream 68.Appropriate processes controller 74 is used to monitor and regulate the volume flow rate of various fuel, combustion air and process stream 57,61 and 68.Process controller 74 can be regulated flow rate through one or more flow regulators 54,65 of automatic control and 73a-c.Perhaps, but one or more flow regulators 54,65 of manual adjustments and 73a-c.
Adam's apple structure 58 is arranged on the upstream extremity 38 of cup 42, and in one embodiment, comprises annular wall 76, this annular wall 76 from two ends towards throat's 78 inside polymerizations that area of section reduces or dwindle.Adam's apple structure 58 is arranged on volution blade 60 downstream, makes the combustion air flow 61 that discharges through volution blade 60 before getting into cup 42, must pass Adam's apple structure 58.The internal diameter of throat 78 can be roughly the same with the internal diameter of the ring 63b that volution blade 60 is installed.
During start-up mode, fuel terminal 56 is arranged to make fuel stream 57 to discharge from fuel terminal 56 in the primary importance in the center line downstream of throat 78.Combustion air flow 61 discharges from volution blade 60 in the second place of the first exhaust position upper reaches pre-selected distance of fuel stream 57, thereby two streams at first mix at throat 78 places or its downstream.Under the combustion air and fuel ratio of pre-selected, fuel terminal 56 is in the alignment restrictions fuel in throat 78 downstream and mixing of combustion air fully, and makes local burnup's concentration in combustible range, makes fuel in cup 42, burn with the flame mode.According to flox condition, flame can extend in the upstream portion of oxidizing chamber 12 from cup 42.When hot combustion gas stream peroxidating chamber 12, the refractory liner 16 of oxidizing chamber 12 is heated to the temperature of pre-selected, this temperature can be kept the special fuel that flows through oxidizing chamber 12 and the Flameless thermal oxidation of air mixture.When using natural gas to act as a fuel the source, confirmed that this method is in the extremely interior successful operation of pre-selected temperature range of about 2,400 ° of F of about 1,900 ° of F.Along with further optimization, believe that the pre-selected temperature range can expand to from about 1,700 ° of F to about 3,000 ° of F to this equipment and method.
After refractory liner 16 reached the pre-selected temperature, this process switched to the Flameless thermal oxidation pattern from start-up mode, and in this pattern, each composition of fluid stream 11 that is transported to oxidizing chamber 12 is by thermal oxide.Can during carrying out the transition to the Flameless thermal oxidation pattern, make the flame that ins all sorts of ways in the quenching fluid stream 11 from start-up mode.In the embodiment shown, the switching that realizes from start-up mode to the Flameless thermal oxidation pattern through the fuel terminal 56 that moves throat 78 upper reaches.Should moving of fuel end 56 make fuel stream 57 discharge from fuel terminal 56 in the second place, and this impinges upon in the burner throat 78 fuel of discharging fuel terminal 56.Fuel stream 57 is in contact with one another in the position at throat 78 upper reaches with whirlpool combustion air flow 61, thereby fuel stream 57 can more fully be mixed with combustion air flow 61.Because mixing more fully of fuel stream 57 and combustion air flow 61, the air of whole mixture is lower than lower flammable limit to fuel ratio, and in cup 42, eliminates visible flame.As an alternative method, the fuel of carrying through injection tip 70 can be used for start-up mode.In this embodiment, fuel terminal 56 is fixed on the position at throat 78 upper reaches, and the fuel valve (not shown) switches to fuel terminal 56 with fuel from injection tip 70 after reaching the pre-selected temperature.In either case; Because heat from oxidizing chamber 12 interior refractory liners 16 transmission; Fuel and combustion air mixture continue in oxidizing chamber 12, to carry out Flameless thermal oxidation; And need not flue gas recirculation, the preheating of fuel stream, combustion air flow and/or process stream 57,61 or 68, and/or need not as desired in the prior art process, in oxidizing chamber 12, to use the bed matrix.After visible flame extinguished, the NOx content in the flue gas significantly descended, comprise drop to less than 5, less than 2 and even less than the 1ppm dry weight, and CO content does not have increase.When not using fuel staging, sustainable realization is less than the NOx content of 2ppm dry weight with less than the CO content of 1ppm dry weight under the operating temperature up to 2,380 ° of F.Even 14.4% fuel staging is arranged, under the running temperature of 1990 ° of F, also realized the NOx content of 6-12ppm dry weight and less than the CO content of 1ppm dry weight in visible flame.The thermal oxide release heat of other composition in fuel and the fluid stream 11, this heat continues to heat refractory liner 16 again.According to concrete process condition and composition, the time that the heat time-continuing process that is discharged can be moved under the Flameless thermal oxidation pattern.Under some condition and composition, think this process in the thermal oxide pattern from time of keeping endless.
Should be appreciated that and also can otherwise realize through promoting fuel stream 57 and preventing that local concentration is in combustible range and switch to no flame oxidation pattern from start-up mode mixing of combustion air flow 61.For example; As previously mentioned; Except using the single fuel gun 48 that is axially moveable, also can use from second fuel of terminal 56 axial translations of first fuel terminal, thereby can flow 57 at different axial location burner oils with respect to the exhaust position of Adam's apple structure 58 and combustion air flow 61.During start-up mode, through mixing with the thorough of combustion air flow 61 to prevent fuel stream 57 near the terminal burner oil stream 57 of the fuel of Adam's apple structure 58.During the Flameless thermal oxidation pattern, fuel stream 57 is led to another fuel end so that fuel stream 57 mixes with combustion air flow 61 more fully then.
In addition; Or alternatively; In order to promote mixing of fuel stream 57 and combustion air flow 61, during carrying out the transition to the Flameless thermal oxidation pattern, can change the combustion air of part and the ratio of fuel through only changing fuel stream 57 relative flow rates with respect to combustion air flow 61 from start-up mode.During start-up mode, the ratio of partial combustion air and fuel is in combustible range.In order to carry out the transition to the Flameless thermal oxidation pattern, the ratio of scalable combustion air and fuel makes local ratio be enough to outside flammable range, to extinguish employed visible flame during start-up mode.
Surpass turbulent flame speed and be and carry out the transition to the conventional method that extinguishes visible flame during the Flameless thermal oxidation pattern.During start-up mode, fuel stream 57 remains on below the upper limit of turbulent flame speed with the flow rate of combustion air flow 61.During no flame oxidation pattern; Improve one or both flow rates in fuel stream 57 and the combustion air flow 61; Thereby mixture flows with the flow rate that is higher than turbulent flame speed, and knock down the flame is also owing to the heat transmission from refractory liner 16 makes fuel and combustion air mixture at oxidizing chamber 12 internal heating oxidations thus.Again for example, except the flow rate with fuel and combustion air mixture is increased to the speed more than the turbulent flame speed, also can turbulent flame speed be reduced to below the flow rate of fuel and combustion air mixture.This can realize through variety of way.For example, former state mode and carry out the transition to the Flameless thermal oxidation pattern from start-up mode during, can be through such as moving the internal flow geometrical property that position that fuel sprays change burner 24.Again for example, can keep the structure (not shown) to be arranged in the cup 42 flame with the retention flame during start-up mode.During carrying out the transition to no flame oxidation pattern, can flame be kept structure to move or changes reducing turbulent flame speed then, thus the retention flame no longer.
Such as when being cooled at refractory liner 16 in oxidizing chamber 12, need additional heat to flow the Flameless thermal oxidation of each composition in 11 to keep fluid below the desired temperature, this process also can circulate between start-up mode and no flame oxidation pattern in the pre-selected time interval.This cooling can be caused by the heat loss of the shell 14 through oxidizing chamber 12 or caused by the cooling effect of fuel, combustion air and/or process stream 57,61 and 68.
According to the condition of employed detailed process and equipment, Flameless thermal oxidation can be kept such as one hour or longer a period of time (comprising endless) certainly.As noted above; In other is used, maybe to oxidizing chamber 12 increase additional heat with compensation through the heat loss of shell 14 with under being lower than the temperature of not having flame oxidation, be transported to one or more cooling effect in fuel, combustion air and/or process stream 57,61 and 68 of burner 24 or oxidizing chamber 12.Can be through continuously or off and on pre-heating fuel, combustion air and/or process stream; Through postcombustion being introduced oxidizing chamber 12 such as the injection tip 71 of a part that has or do not have process stream 68 and/or one or more injection tips of injection tip 72; Through with flame modes burning postcombustion, increase additional heat through the use stratie and/or through under the initial heating pattern, moving burner 24 off and on.Through increase this additional heat with the visible flame combustion fuel NOx and CO content are increased, but total body burden can keep significantly being lower than through moving the content that thermal oxidizer 10 is produced with all fuel of visible flame mode sustained combustion.
At thermal oxidizer 10 during no flame oxidation mode operation; Comprise that fuel and combustion air flow 57 and 61 are transported to oxidizing chamber 12 with the fluid stream of optional process stream 68 11 as premixed mixture, the ratio of combustion air and fuel is for the desired service condition selection of ongoing concrete application.The corresponding flow rate of combustion air and fuel ratio and combustion air flow 61 and fuel stream 57 is adjusted to the enough heat that thermal oxide produced of supply by other composition of fuel and fluid stream 11 usually, thereby thermal oxidation process is kept desired duration.In addition; Local burnup's concentration that partial combustion air and fuel ratio or fluid flow in 11 should be lower than the lower flammable limit for employed special fuel or fuel mixture, and perhaps one or more flow rate adjustment becomes the flow rate of fluid stream 11 to flow more than the turbulent flame speed of other flammable composition in 11 at fuel and fluid in fluid stream 11, combustion air flow 61 and the fuel stream 57.For example, when use comprises that the natural gas of about 95% methane acts as a fuel, can use to be about 20: 1 or higher combustion air and fuel ratio.As long as combustion air and fuel concentration cup 42 under its mixture temperature beyond combustible range, and flow through abundant premixed in the fluid stream 11 of oxidizing chamber 12, then the thermal oxide of generation is exactly aphlogistic in oxidizing chamber 12.Can be expelled in the cup 42 to reduce fuel concentration and to remain on thus below the lower flammable limit with excess air and/or such as the diluent of nitrogen, carbon dioxide and/or water vapour to reduce the nonconforming probability in the cup 42 that is tempered to.Chokes portion 44 (if any) flows into the speed of the fluids stream 11 in the oxidizing chambers 12 and cup 42 is further reduced the probability of tempering with the radiation shield that sends from oxidizing chamber 12 through increasing from cup 42.The existence of diluent can improve fuel efficiency because do not have the flame process can be in combustion air flow oxygen content operation when low.
Each composition of the fluid of thermal oxide stream 11 can be any composition that can stand thermal oxide in above-mentioned no flame process, such as fuel, waste materials, organic compound (comprising VOC and half volatile organic compound) and various types of hazardous air pollutants.Under the situation that requires thermal oxidizer 10 only to move as burner, one or more fuel can be used as the composition of the fluid stream 11 that stands thermal oxide.In other words, the present invention comprises thermal oxidizer 10 wherein and is not used in the process of removing pollutant from process stream, but as providing as the low NOx of the hot flue gas on its way (such as upstream device 31) and the situation of low CO burner.
Process of the present invention need not used United States Patent (USP) the 5th, 165, the bed substrate of institute's type of service in No. 884.Therefore, the flowing of fluid stream 11 that can be used for carrying out Flameless thermal oxidation all or almost all of the open interior volume 18 of oxidizing chamber 12.So, in this process, avoided the shortcoming of the bed substrate of previous discussion, this process can also realize low-down NOx and CO content.Although bed substrate is unnecessary in Flameless thermal oxidation process of the present invention, it is desirable in some cases to comprise that non-streamline body or other mixing arrangement in the oxidizing chamber 12 is with the mixing that promotes fluid stream 11 and/or the flame (if you are using) of stable supplying additional heat.The flame that non-streamline body or other mixing arrangement also can be used as in the cup 42 keeps structure.As previously mentioned; Change or movable flame keeps structure can change the turbulent flame speed that fluid flows 11 fuel, with promote therein fuel with the visible flame mode burn with the pattern of initial heating or preheating oxidizing chamber refractory liner 16 and wherein fuel do not have by the transition between the pattern of flame ground thermal oxide through heat transmission from refractory liner 16.
Can the smoke reaction product of discharging oxidizing chamber 12 be transported to exhaust chimney 30 to lead to atmosphere.Flue gas also can be used as heat exchange medium one or more compositions with preheating fluid stream 11 before being transported to oxidizing chamber 12.In addition, hot flue gas can be used in the upstream device 31 such as process heater, boiler, reactor furnace, reactor furnace such as cracking of ethylene unit, hydroforming device etc.
With by way of example following instance is provided, these instances are not represented the restriction to overall range of the present invention.
Instance 1
With 114, the flow rate of 000scf/hr is transported in the cup 42 combustion air of air form through volution blade 60 under the room temperature.With 5, the flow rate of 550scf/hr is injected in the cup 42 fuel of natural gas form through fuel terminal 56 under the room temperature.Fuel and combustion air mixture are lighted and burnt with visible flame, reach up to oxidizing chamber 12 till the temperature of 1,880 ° of F.In case oxidizing chamber 12 like this by preheating, then makes fuel and combustion air before mixture being passed burner throat 78, more fully mix to come extinguish combustion device flame through terminal 56 center lines from burner throat 78 of fuel being retracted about 3.5 inches.Fuel and combustion air flow rate almost remain unchanged, and the pre-mixed stream of fuel and combustion air feeds cups 42 and do not have visible flame through burner throat 78, and have also disappeared in the fuel combustion noise of being supervened of in flame modes, burning.Because from the heat transmission of the refractory liner 16 of the preheating of oxidizing chamber 12, fuel continues oxidized in stable no flame oxidation process.No flame oxidation process roughly is in balance, and record NOx content less than 1ppm dry weight and CO content less than the 1ppm dry weight.This process carried out 8.5 hours and the temperature in the oxidizing chamber 12 in burner 24 back to back downstream because the heat loss of the shell 14 through oxidizing chamber 12 and turning off when being cooled to the temperature of 1,500 ° of F with the cooling effect that environment temperature is transported to fuel and the combustion air of burner 24.When process was turned off, the outlet temperature of oxidizing chamber 12 still was in 1,880 ° of F.
Instance 2
Change following parameter, repeat the test of instance 1: (1) combustion air flow rate is reduced to 100,200scf/hr, and (2) are through reducing fuel staging the fuel flow rate through cup 42.Total fuel flow speed is 5; 500scf/hr; And be divided into 85.6% fuel in being ejected into cup 42 before with all combustion air flow premixeds, and two flue gases terminal 72 of the oxidizing chamber 12 in the back to back downstream of remaining 14.4% fuel through being arranged on burner 24 spray.Be ejected into fuel in the oxidizing chamber 12 with the visible flame burning and be arranged to directly to heat refractory liner 16 through the flue gas end stablize the interior no flame oxidation process of oxidizing chamber 12.Because the input of the heat of this increase, the outlet temperature of oxidizing chamber 12 is 1,990 ° of F.Because the part of fuel is burnt with visible flame, so NOx content increases and changes from 6 to 12ppm dry weights.CO content remains on below the 1ppm dry weight.Deliberately when operation in 44.5 hours, stop and to test, look that this process is from keeping.
Test demonstration subsequently can be through realizing about 2,000 ° of F, 2 with fuel staging to each gas end in burner 24 downstream; 100 ° of F, 2; 200 ° of F, 2,300 ° of F and 2,400 ° be F's even higher running temperature and be no more than the inflammable limit value in the cup 42.Even under the flow rate that makes oxidizing chamber 12 inner fluids stream 11 and classification fuel intimate admixture under the temperature of about 2,000 ° of F, also realized being lower than the NOx and the CO content of 1ppm dry weight.Believe also and can realize higher temperature.
Instance 3
The test case that instance 3 is appeared confirms under the situation after refractory material 16 abundant preheatings, surpasses turbulent flame speed to allow more than the lower flammable limit of air/fuel mixture in cup 42, the not having flame operation.The combustion air flow rate is 245,640scf/hr, and the natural gas flow rate is 18,357scf/hr, and the thermal oxidizer running temperature is 2,381 ° of F.Premixed is to realize the pre-mixed fuel composition of 5.87 volume % in cup 42 for combustion air and natural gas, and this is higher than environment temperature lower flammable limit (5 volume %).This oxidizing process is not to cup 42 tempering, and expression has surpassed the turbulent flame speed that reduces passage 45 through diameter.NOx discharging to this process condition is the 1.3ppm dry weight, and CO discharges not detectable (＜1ppm dry weight).
Instance 4
Through with 20, the CO of 820scf/hr
2With 62, the O of the fresh air combination results 14.5 volume % of 280scf/hr
2Content produces low O thus
2The mixture of combustion air.To hang down O through volution blade 60
2Combustion air is transported in the cup 42.With 5, the flow rate of 475scf/hr is injected in the cup 42 fuel of natural gas form through fuel terminal 56 under the room temperature.Fuel and low O
2Combustion air mixes in cup 42 and is discharged to not to be had in the thermal oxidizer 12 of flame oxidation fuel.Since this oxidation, the O in the flue gas of generation
2Concentration is 2 volume % dry weights, and CO concentration can not be surveyed, and NOx concentration is the 1.2ppm dry weight in the flue gas, and running temperature is 1,941 ° of F.This test case has confirmed that thermal oxidizer 10 usefulness hang down O
2Combustion air flow, flue gas recirculation flow and/or hang down the ability of heat value waste gas stream operation.This test also shows with conventional flame type burner to be compared, and no flame process will be hanged down O in combustion air
2Content is operation down.When using O
2Can obtain the thermal efficiency during the low combustion air source of content, flow and keep stable because need less fresh air be added to low O2 content.Normal burner needs to be higher than in the combustion air under the environment temperature O of 18 volume % usually
2Carrying out stable operation, and this test has confirmed with 14.5 volume %O in the combustion air
2Stable operation.
From preceding text, can find out, the present invention can realize well above-mentioned all purposes and target and this structure intrinsic other advantage.
Should be appreciated that some characteristic and son combination are available, and can not relate to other structure and son adopts in combination.This is also contained in the scope of the present invention.
Owing to can carry out multiple possible embodiment and not depart from its scope, so be to be understood that to set forth all should be interpreted as and explain and unrestricted implication with all the elements shown in the accompanying drawing at this to the present invention.
Claims (56)
1. method that is used for each composition of Flameless thermal oxidation in having the oxidizing chamber of interior lining said method comprising the steps of:
(a) at first heat said oxidizing chamber lining; And
(b) under the condition of the thermal oxide that starts said composition owing to heat transmission, said composition is transported to said oxidizing chamber then from said heated oxidizing chamber lining.
2. the method for claim 1 is characterized in that, the said step that said composition is transported to said oxidizing chamber comprises the step that said each composition is transported to said oxidizing chamber in fluid stream.
3. method as claimed in claim 2 is characterized in that, is included in during the said thermal oxide of said composition or afterwards said fluid is flow through the step of said oxidizing chamber.
4. method as claimed in claim 3; It is characterized in that being included in provides one or more fuel when said fluid stream passes said oxidizing chamber and keep condition in the said oxidizing chamber with owing to transmit and the step of said one or more fuel in the said fluid stream of thermal oxide from the said heat of said oxidizing chamber lining in the said composition of said fluid stream.
5. method as claimed in claim 4; It is characterized in that the step of said one or more fuel during the condition in the said oxidizing chamber of said maintenance flows with the said fluid of thermal oxide is included in when said fluid stream passes said oxidizing chamber and makes the local concentration of said one or more fuel of said fluid stream be lower than lower flammable limit.
6. method as claimed in claim 5 is characterized in that, comprises through changing said condition in the said oxidizing chamber so that the step that said one or more fuel combustions in the said fluid stream heat said oxidizing chamber lining again.
7. method as claimed in claim 6 is characterized in that, the step of said condition comprises that the local concentration with said one or more fuel changes to more than the said lower flammable limit in the said oxidizing chamber of said change.
8. method as claimed in claim 4; It is characterized in that the condition in the said oxidizing chamber of said maintenance comprises the passage that makes said fluid stream flow through reduced with the flow rate of the turbulent flame speed that is higher than said one or more fuel with the step of said one or more fuel in the said fluid stream of thermal oxide.
9. method as claimed in claim 8 is characterized in that, comprises through changing said condition in the said oxidizing chamber so that the step that said one or more fuel combustions in the said fluid stream heat said oxidizing chamber lining again.
10. method as claimed in claim 9 is characterized in that, changes the said step of said condition in the said oxidizing chamber and comprises that the flow rate with said fluid stream changes to below the said turbulent flame speed of said one or more fuel.
11. the method for claim 1 is characterized in that, the said step that at first heats said oxidizing chamber lining is included under the condition that makes said composition burning said composition is transported to said oxidizing chamber.
12. method as claimed in claim 11 is characterized in that, the said step that at first heats said oxidizing chamber lining comprises said composition is transported to said oxidizing chamber in fluid stream.
13. method as claimed in claim 12 is characterized in that, the said step that at first heats said oxidizing chamber lining is included in the step that one or more fuel are provided in the said composition of said fluid stream.
14. the method for claim 1; It is characterized in that; Comprise and make the fluid stream that comprises one or more fuel under primary condition, flow through said oxidizing chamber so that said one or more fuel combustions producing the initial heating of said oxidizing chamber lining, and change said condition with owing to the step that produces the said thermal oxide of said composition from the heat transmission of said oxidizing chamber lining then.
15. method as claimed in claim 14 is characterized in that, the said step that said composition is transported to said oxidizing chamber comprises carries the said composition that comprises said one or more fuel.
16. method as claimed in claim 15 is characterized in that, comprises the said condition of further change so that said oxidizing chamber lining is also heated in said one or more fuel combustions again.
17. method as claimed in claim 16 is characterized in that, be included in said composition said thermal oxide said step and heat the step that circulates between the said step of said oxidizing chamber lining again.
18. method as claimed in claim 14 is characterized in that, the said step that changes said condition comprises that the local concentration with said one or more fuel changes to outside the said combustible range in the combustible range of said one or more fuel.
19. method as claimed in claim 18; It is characterized in that; Comprise the step of promoting the mixing of said one or more fuel in the said fluid stream, in the combustible range of said one or more fuel, change to the said step outside the said combustible range with the local concentration that produces said one or more fuel.
20. method as claimed in claim 14 is characterized in that, the step of the said condition of said change comprises that the flow rate with said fluid stream changes to more than the said turbulent flame speed below the said turbulent flame speed of said one or more fuel.
21. method as claimed in claim 4 is characterized in that, comprises that the hazardous air pollutants with the said composition that flows as said fluid is included in interior step.
22. method as claimed in claim 21 is characterized in that, comprises the step of adding said hazardous air pollutants to said fluid stream from process stream.
23., it is characterized in that said hazardous air pollutants comprises VOC and half volatile organic compound like claim 21 or 22 described methods.
24. method as claimed in claim 23 is characterized in that, is included in the step that said fluid stream is added at least a portion of said process stream at the position in the said oxidizing chamber.
25. method as claimed in claim 23 is characterized in that, is included in said fluid stream is transported to the step that said oxidizing chamber adds at least a portion of said process stream to said fluid stream before.
26. method as claimed in claim 5 is characterized in that, is included in said fluid stream is transported to said oxidizing chamber before with at least a portion of said one or more fuel and the premixed step of combustion air in the said fluid stream.
27. method as claimed in claim 26; It is characterized in that, comprise another fluid stream that comprises one or more fuel in the said fuel is introduced said oxidizing chamber and said one or more fuel in said another fluid stream of said oxidizing chamber internal combustion so that said oxidizing chamber is increased additional heat.
28. the method for claim 1 is characterized in that, comprises the step of said thermal oxide maintenance greater than one hour period.
29. method as claimed in claim 4; It is characterized in that, in the said composition of said fluid stream, provide the said step of one or more fuel to comprise to provide one or more the fuel that is selected from following group: natural gas, refinery fuel gas, hydrogen, other hydrocarbon and composition thereof.
30. method as claimed in claim 4; It is characterized in that, in the said composition of said fluid stream, provide the said step of one or more fuel to comprise to provide one or more the fuel that is selected from following group: refinery fuel gas, hydrogen, methane, ethane, propane, butane, other hydrocarbon, and composition thereof.
31., it is characterized in that said refinery fuel gas comprises carbon monoxide like claim 29 or 30 described methods.
32. method as claimed in claim 31 is characterized in that, is included in the step of adding one or more diluents in the said fluid stream.
33. method as claimed in claim 4 is characterized in that, in the said composition of said fluid stream, providing the said step of one or more fuel to comprise natural gas is included in as one of said one or more fuel.
34. method as claimed in claim 3 is characterized in that, is included in to make said fluid flow through the step of at least a portion in the said fluid stream of preheating before the said step of said oxidizing chamber.
35. method as claimed in claim 4 is characterized in that, the said step that at first heats said oxidizing chamber lining comprises said oxidizing chamber lining is heated to the temperature in 1,800 to 3,000 ° of F scope.
36. method as claimed in claim 35 is characterized in that, comprises the step of natural gas in the said composition that provides the said step of one or more fuel to be included in said fluid stream.
37. the method for claim 1; It is characterized in that; The said step that at first heats said oxidizing chamber lining comprises through forming hot flue gas at one or more fuel of burner internal combustion with said oxidizing chamber fluid flow communication, and said hot flue gas is transported in the said oxidizing chamber said lining is heated to the step of pre-selected temperature.
38. method as claimed in claim 37; It is characterized in that, be included in during the said step that at first heats said lining in the said oxidizing chamber second place of said one or more fuel pre-selected distance in primary importance is introduced said burner cavity and at the said primary importance upper reaches is introduced combustion air or another oxidant in the said inner chamber.
39. method as claimed in claim 38 is characterized in that, comprises said one or more fuel are mixed with said combustion air so that said composition carries out the step of said thermal oxide in said oxidizing chamber more fully.
40. method as claimed in claim 2 is characterized in that, comprises the step that prevents the recirculation of said fluid stream.
41. the method for claim 1 is characterized in that, is included in to keep said condition during the said thermal oxide of said composition to obtain less than the NOx content of 12ppm dry weight with less than the CO content of 1ppm dry weight.
42. the method for claim 1 is characterized in that, is included in to keep said condition during the said thermal oxide of said composition to obtain less than the NOx content of 5ppm dry weight with less than the CO content of 1ppm dry weight.
43. the method for claim 1 is characterized in that, is included in to keep said condition during the said thermal oxide of said composition to obtain less than the NOx content of 1ppm dry weight with less than the CO content of 1ppm dry weight.
44. one kind is used for the method that in the oxidizing chamber with internal refractory lining Flameless thermal oxidation comprises each composition of fluid stream of one or more fuel, said method comprising the steps of:
(a) but fluid stream and the combustion air that comprises the thermal oxide composition is provided, but said thermal oxide composition comprises one or more fuel;
(b) in said oxidizing chamber, said refractory liner is heated to the pre-selected temperature; And
(c) then owing to from the heat transmission of said refractory liner and the said composition of thermal oxide does not have to make said fluid stream pass said oxidizing chamber under the condition of recirculation of said fluid stream.
45. method as claimed in claim 44 is characterized in that, comprises successively repeating step (b) and (c).
46. method as claimed in claim 44 is characterized in that, the said step that provides fluid to flow comprises provides the fluid that comprises methane and combustion air stream.
47. method as claimed in claim 44; It is characterized in that; Heat in the said oxidizing chamber the said step of said refractory liner and comprise through forming hot flue gas, and said hot flue gas is transported in the said oxidizing chamber said lining is heated to the step of said pre-selected temperature with said one or more fuel of the burner internal combustion of said oxidizing chamber fluid flow communication.
48. method as claimed in claim 47; It is characterized in that, be included in the said oxidizing chamber of heating during the said step of said lining the second place of said one or more fuel pre-selected distance in primary importance is introduced said burner cavity and at the said primary importance upper reaches is introduced combustion air the step in the said inner chamber.
49. method as claimed in claim 48; It is characterized in that, comprise said one or more fuel and said combustion air are mixed to stop the step that thermal oxide that the burning of said one or more fuel in said burner make said one or more fuel simultaneously can start owing to the heat transmission from said refractory liner in the said oxidizing chamber more fully.
50. method as claimed in claim 47; It is characterized in that the said step that under the condition that makes said composition thermal oxide, makes said fluid stream pass said oxidizing chamber comprises the step of local concentration beyond the combustible range of said one or more fuel that makes said one or more fuel in the said fluid stream.
51. method as claimed in claim 50; It is characterized in that, comprise through said local concentration changing to the step that makes said one or more fuel combustions in the said combustible range of said one or more fuel and heat said refractory liner again one or more fuel described in the said fluid stream.
52. method as claimed in claim 47; It is characterized in that the said step that under the condition that makes said composition thermal oxide, makes said fluid stream pass said oxidizing chamber comprises that the flow rate that makes said fluid stream is higher than the turbulent flame speed of one or more fuel described in the said fluid stream.
53. method as claimed in claim 52 is characterized in that, comprises through the said flow rate with said fluid stream being reduced to below the said turbulent flame speed so that said one or more fuel combustions heat the step of said refractory liner again.
54. method as claimed in claim 44 is characterized in that, is included in after the said thermal oxide of said composition from said oxidizing chamber to remove said fluid stream and said fluid stream is transported to the step of upstream device.
55. a thermal oxidizer comprises:
Oxidizing chamber, said oxidizing chamber comprise the shell that limits the open interior volume and have upstream extremity and downstream and lining; And
The device of thermal oxide when being used for heating said lining and being used to make the composition of fluid stream to be present in said open interior volume, said thermal oxide is owing to the heat transmission from said lining is carried out.
56. thermal oxidizer as claimed in claim 55; It is characterized in that; Said device is included in the burner of the said upstream extremity of said shell, is used for one or more fuel of said fluid stream that at first burn, thereby heats said lining and said one or more compositions of thermal oxide.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/945,775 US20090136406A1 (en) | 2007-11-27 | 2007-11-27 | Flameless thermal oxidation method |
| US11/945,775 | 2007-11-27 | ||
| US12/273,367 | 2008-11-18 | ||
| US12/273,367 US20090133854A1 (en) | 2007-11-27 | 2008-11-18 | Flameless thermal oxidation apparatus and methods |
| PCT/US2008/084637 WO2009070563A1 (en) | 2007-11-27 | 2008-11-25 | Flameless thermal oxidation apparatus and methods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101874180A CN101874180A (en) | 2010-10-27 |
| CN101874180B true CN101874180B (en) | 2012-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801186797A Expired - Fee Related CN101874180B (en) | 2007-11-27 | 2008-11-25 | Flameless thermal oxidation apparatus and methods |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20090133854A1 (en) |
| EP (1) | EP2227654A1 (en) |
| JP (1) | JP2011508864A (en) |
| KR (1) | KR20100098632A (en) |
| CN (1) | CN101874180B (en) |
| AR (1) | AR069751A1 (en) |
| BR (1) | BRPI0820661A2 (en) |
| CA (1) | CA2705773A1 (en) |
| CL (1) | CL2008003517A1 (en) |
| MX (1) | MX2010005194A (en) |
| TW (1) | TW200940155A (en) |
| WO (1) | WO2009070563A1 (en) |
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| CN102809162B (en) * | 2012-08-08 | 2016-03-30 | 陈汉笙 | The two-way thermal oxidizer of a kind of nonflame |
| US9476589B2 (en) | 2013-03-13 | 2016-10-25 | Fives North American Combustion, Inc. | Diffuse combustion method and apparatus |
| US10215408B2 (en) | 2015-12-09 | 2019-02-26 | Fives North American Combustion, Inc. | Method and apparatus for diffuse combustion of premix |
| EP3242080B1 (en) * | 2016-05-04 | 2019-07-10 | WS-Wärmeprozesstechnik GmbH | Apparatus and method for heating of furnaces using radiant tubes |
| DE102017222517A1 (en) * | 2017-12-12 | 2019-06-13 | Dürr Systems Ag | Method for cleaning exhaust gas and exhaust gas purification device |
| EP3650753B1 (en) | 2018-11-12 | 2022-11-09 | WS Wärmeprozesstechnik GmbH | Method and device for flameless staged combustion |
| EP4055066A1 (en) * | 2019-11-07 | 2022-09-14 | ExxonMobil Chemical Patents Inc. | Olefin polymerization processes |
| US11898747B2 (en) | 2020-04-30 | 2024-02-13 | Honeywell International Inc. | Burner system and process for natural gas production |
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- 2008-11-25 WO PCT/US2008/084637 patent/WO2009070563A1/en active Application Filing
- 2008-11-25 JP JP2010536115A patent/JP2011508864A/en not_active Withdrawn
- 2008-11-25 KR KR1020107013157A patent/KR20100098632A/en active IP Right Grant
- 2008-11-25 EP EP08853951A patent/EP2227654A1/en not_active Withdrawn
- 2008-11-25 BR BRPI0820661-9A patent/BRPI0820661A2/en not_active IP Right Cessation
- 2008-11-25 CA CA2705773A patent/CA2705773A1/en not_active Abandoned
- 2008-11-25 MX MX2010005194A patent/MX2010005194A/en not_active Application Discontinuation
- 2008-11-25 CN CN2008801186797A patent/CN101874180B/en not_active Expired - Fee Related
- 2008-11-26 AR ARP080105140A patent/AR069751A1/en not_active Application Discontinuation
- 2008-11-26 CL CL2008003517A patent/CL2008003517A1/en unknown
- 2008-11-26 TW TW097145644A patent/TW200940155A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2705773A1 (en) | 2009-06-04 |
| JP2011508864A (en) | 2011-03-17 |
| AR069751A1 (en) | 2010-02-17 |
| WO2009070563A1 (en) | 2009-06-04 |
| TW200940155A (en) | 2009-10-01 |
| EP2227654A1 (en) | 2010-09-15 |
| US20090133854A1 (en) | 2009-05-28 |
| KR20100098632A (en) | 2010-09-08 |
| CN101874180A (en) | 2010-10-27 |
| MX2010005194A (en) | 2010-05-24 |
| BRPI0820661A2 (en) | 2015-06-16 |
| CL2008003517A1 (en) | 2010-01-15 |
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