CN1429129A - Method and device for catalytic conversion of substance - Google Patents
Method and device for catalytic conversion of substance Download PDFInfo
- Publication number
- CN1429129A CN1429129A CN01809312A CN01809312A CN1429129A CN 1429129 A CN1429129 A CN 1429129A CN 01809312 A CN01809312 A CN 01809312A CN 01809312 A CN01809312 A CN 01809312A CN 1429129 A CN1429129 A CN 1429129A
- Authority
- CN
- China
- Prior art keywords
- catalytically
- active materials
- fuel
- waste gas
- catalyst assembly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1208—Inorganic compounds elements
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2610/00—Adding substances to exhaust gases
- F01N2610/01—Adding substances to exhaust gases the substance being catalytic material in liquid form
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2610/00—Adding substances to exhaust gases
- F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
For the conversion of a substance in a gas flow (A), it is feeded into a reaction space (2), and the substance (NO) is exposed to the action of catalytic effecting material (K, KU). With the gas flow (A), into the reaction space (2) is supplied with an agent (S) which is the catalytic effecting material (K, KU), or can be formed by the catalytic effecting material (K, KU). Preferably, the agent (S) is mixed with the fuel (B). In its burning, the substance (NO) contained in the gas flow (A) is produced as exhaust gas. In the method for reactivating a deactivated catalyst module (3), the catalyst module is moistured with an agent (S), which is a fresh catalytic effecting material (KU), or contain this material, or able be deposited from such material. Both methods are especially based on the principle of selective catalytic reduction, and can be used to decompose the nitrogen oxide (NO) in the waste gas (A). It also mentions a fuel (B) containing an agent which is the catalytic effecting material, or produced from the catalytic effecting material (KU) when it is burned.
Description
The present invention relates to catalyst field.
The present invention relates to a kind of method that is used for transforming the air-flow material, in particular for the conversion of nitrogen oxides Cheng Shui in according to selective catalytic reduction reaction flue gas a kind of and that ammonia mixes being flowed and the method for nitrogen, wherein, described air-flow is transported in the catalytic reduction reaction chamber, and this is subjected to a kind of catalytic action of catalytically-active materials by transformation substance.
The invention still further relates to a kind of method that makes a kind of catalyst assembly reactivation to the small part loss of catalytic activity, a kind of catalytic action material layer is manufactured to come out this catalyst assembly by depositing in a catalyst substrate or on it.This method is particularly useful for making a kind of catalyst assembly reactivation according to the work of selective catalytic reduction reaction mode, to be reduced in the nitrogen oxide in a kind of flue gas.
The present invention also relates to a kind of being used in a combustion process burnt fuel in addition.
In addition, the invention still further relates to a kind of waste gas purification apparatus, in particular for the combustion apparatus in power plant or the waste gas purification apparatus of vehicle internal combustion engine, wherein, the waste gas stream that burning produces flows through a catalyst assembly, transforming wherein contained harmful substance, this catalyst assembly by a kind of catalysis material of facilitating the harmful substance catalyzed conversion is deposited in the catalyst substrate or on manufactured come out.Wherein, especially nitrogen oxides in exhaust streams can be transformed according to the selective catalytic reduction reaction principle.
The invention still further relates to another kind and be particularly useful for the combustion apparatus in power plant or the waste gas purification apparatus of vehicle internal combustion engine, wherein, the waste gas stream that burning produces flows through a catalyst assembly, transforming wherein contained harmful substance, this catalyst assembly is by being deposited on a kind of catalysis material of facilitating the harmful substance catalyzed conversion in one catalyst substrate or manufactured come out on it.Wherein, especially nitrogen oxides in exhaust streams can be transformed according to the selective catalytic reduction reaction principle.
When oxidizing fire mineral substance fuel, generate to comprise environment is caused the material of burden or the waste gas or the flue gas of harmful substance.For example in the useless flue gas that incineration firing device, power plant, smelting furnace or heating station produce, contain nitrogen oxide, for example nitric oxide or nitrogen dioxide.Burning diesel oil or other fuel also can produce the waste gas or the fluid of similar type in vehicle internal combustion engine.
For example be entitled as in the description of " selektive katalytische Reduktion (SCR: selective catalytic reduction) " or in Germany Patent document DE 24 58 888, disclose the related content that transforms the nitrogen oxide that is not expected to have in the product description acceptance of the bid that Siemens Company's job number in 1996 is A96001-U11-A294-V1.
According to the method, by adding ammonia nitrogen oxide is catalytically converted into harmless nitrogen and steam.Make useless flue gas or waste gas under 300 to 500 ℃ temperature, pass through a catalyst or a catalyst assembly for this reason.This catalyst assembly is made up of a kind of ceramic matrix or a kind of ceramic catalyst substrates, deposits a catalytically-active materials in this substrate, and it is used for or facilitates conversion of nitrogen oxides is become nitrogen and steam.A kind of like this catalysis material for example is the oxide of titanium, vanadium and/or tungsten and/or molybdenum.
The catalytic activity of known SCR catalyst in its course of work can be weakened according to contained material in the useless flue gas.This is for example caused by chemical aspect reason, that is to say that catalytically-active materials synthesizes a kind of compound that can not participate in the SCR reaction.But also may be because the waste gas stream that catalytically-active materials is flowed is in the course of the work carried under one's arms out from catalyst assembly.Especially when in catalytically-active materials and the waste gas halogen-containing when synthesizing a kind of metal that is easy to flow-halogen compounds, such situation will take place.
The SCR activity of such catalysts is weakened up to now to be compensated like this, that is, increase catalytic amount or add other catalyst assembly.This method is very expensive also very hard.When being applied on the power car, can only after paying the technology effort of being unworthy appreciating, could implement SCR.And in being applied in the power plant time, then need this power plant is closed down.
Therefore, the activity that need take other measure to overcome described catalytically-active materials is weakened this difficult problem.Technical problem to be solved by this invention thereby be for this reason to provide a kind of corresponding method, device and material.
Above-mentioned technical problem solves like this according to the present invention in the method for the described type of preface, that is, a kind of catalytic specie and air-flow are imported in the reduction reaction chamber together, and this material is catalytically-active materials or can constitutes catalytically-active materials by this material.
Preferably insert this catalytic specie continuously.But also can intermittently insert.
Not necessarily need a kind of catalyst assembly when stating method on the implementation.Harmful substance in the catalyzed conversion waste gas can only be carried out with the catalytically-active materials in the material form input reduction reaction chamber by a kind of like this.Can be continuously or import this catalytically-active materials intermittently.
According to a kind of preferred improvement design, allow waste gas flow through or flow through a catalyst substrate that especially is arranged in the reduction reaction chamber.
Preferably the flow direction along waste gas stream added described catalytic specie in this waste gas stream to before it flow to catalyst substrate.
Especially can or after atomizing, add in the waste gas stream described catalytic specie even dispersion ground.
Preferably described catalytic specie is mixed in a kind of fuel, when this fuel combustion, contain hazardous substance produces as waste gas in the gas-flow.
More advantageously filling among the catalyst substrate or a kind of catalytically-active materials of facilitating the harmful substance catalyzed conversion on the deposition thereon, to constitute a catalyst assembly.Before implementing method of the present invention, knownly for example can in an independent production process, make this catalyst assembly by depositing catalytically-active materials.
If the catalytic activity of this catalyst assembly completely or partially disappears, just can utilize the inventive method to make it be close on the spot reactivation (quasi in situ).Therefore, this catalyst assembly that is to say that in order reactivation not necessarily to quit work a power plant need not to be forced to stop production.And for a new or still original catalyst assembly, adopt method of the present invention can prevent from the beginning that then its catalytic activity from being weakened.
According to a kind of preferred improvement and design, described catalytically-active materials that import with air-flow or that constitute by described catalytic specie with when making catalyst assembly, filled wherein so far or the long-pending catalytically-active materials of putting on it identical.Can make the catalyst assembly reactivation effectively thus.
In addition, the described catalytically-active materials that adds in the air-flow or constitute therein itself has catalytic action, like this, even if can not also can promote catalytic efficiency during reactivation at catalyst assembly.
In order to improve the reactivation effect, the catalytically-active materials that has been added in the place ahead of catalyst assembly or have the characteristic that can deposit on the catalyst assembly by the catalytically-active materials that described catalytic specie constitutes.
Equally more advantageously constitute a catalyst assembly on it by being filled into the catalytically-active materials in the air-flow in the catalyst substrate or depositing.
Therefore, utilize method of the present invention at first particularly advantageously a catalyst substrate inertia or catalytically inactive to be placed in the air-flow, by depositing gradually or filling constitute by described catalytic specie or wherein contained catalytically-active materials, constitute catalyst assembly then.
Especially can follow these steps to make catalyst assembly:
A) be mixed in the air-flow as material catalytically-active materials or that include catalytically-active materials or that can therefrom isolate catalytically-active materials a kind of;
B) make this air flow stream cross a catalyst substrate subsequently;
C) by catalytically-active materials being deposited on the catalyst substrate or filling wherein, constitute described catalyst assembly.
Above-mentioned technical problem can also solve like this according to the present invention in the method for the described type of preface, that is, soak catalyst assembly as material catalytically-active materials or that include catalytically-active materials or that can therefrom isolate catalytically-active materials with a kind of.
Therefore, for example at catalyst assembly through after the work of long period, can again catalytically-active materials be placed on the catalyst substrate of catalyst assembly or fill wherein.
Especially the catalytically-active materials in the described material can be filled and/or deposited in the existing catalytically-active materials of having produced when making catalyst assembly at that time.
The catalytically-active materials of having filled wherein or having deposited on it when more advantageously, the catalytically-active materials in the described catalytic specie is with the manufacturing catalyst assembly is identical.
According to a kind of particularly preferred improvement design, described catalytic specie is flowed to catalyst assembly at the catalyst duration of work.A kind of like this on-line operation has special advantage, that is, catalyst assembly needn't quit work for reactivation, thereby also needn't interrupt catalytic reaction process.
Described catalytic specie preferably with in a kind of enter catalyst assembly remains the material that transformed and mixes.Therefore can advantageously need not to allow separately a kind of like this material to be transformed flow to catalyst assembly, because the described material of described catalytic specie in originally will the enter catalyst assembly during with work mixes mutually.
In order to soak catalyst assembly, described catalytic specie preferably is in evaporating state or vaporized state.
According to a kind of preferred variation scheme, described catalytic specie is mixed in a kind of fuel.Produce a kind of material described to be transformed after this fuel combustion as waste gas, this material subsequently in the enter catalyst assembly by catalyzed conversion.
In all above-mentioned methods, catalytically-active materials preferably contains a kind of element atom in these several elements of vanadium, titanium, tungsten, iron and/or molybdenum, and the catalytically-active materials a kind of oxide in these several metals especially.Certainly the mixture of these elements also is fine.
Technical problem to be solved by this invention can solve in a combustion process burnt fuel like this by a kind of being used for, promptly, contain a kind of material in this fuel or be added a kind of material, this material is catalytically-active materials or can generates catalytically-active materials by this material when burning.Therefore described fuel especially can contain catalytically-active materials or be added into catalytically-active materials.
A kind of like this fuel is particularly suitable for the enforcement of the inventive method, and is particularly suitable in those embodiments that use a kind of fuel clearly.Xiang Guan advantage also is applicable to this fuel similarly therewith.
The content of catalytic specie is preferably between 10mg and 200mg described in every kilogram of fuel.
The content of catalytic specie especially can be between 50mg and 100mg described in every kilogram of fuel.
Described catalytic specie, especially catalytically-active materials preferably are comprised in the fuel or by dissolution mechanism or disperse mode with dissolved state or disperse state and are added in the fuel.
Described catalytically-active materials is applicable to that preferably the harmful substance of facilitating burning to produce transforms.
According to a kind of particularly preferred improvement design, described catalytically-active materials has the characteristic that transforms nitrogen oxide according to the SCR principle, and this nitrogen oxide is present in the waste gas that burning produces.
According to fuel another kind of preferred being improved design, described catalytically-active materials contains at least a element in vanadium, titanium, tungsten, iron, the molybdenum or mixing and contains wherein multiple element.
Technical problem to be solved by this invention can solve by a kind of injection apparatus according to the present invention in the described first type waste gas purification apparatus of preface, this injection apparatus can infeed a kind of catalytic specie in the waste gas before waste gas inflow catalyst assembly along the flow direction of waste gas, at this, this material is catalytically-active materials or includes catalytically-active materials or can isolate catalytically-active materials from this material.
Described injection apparatus preferably has a storage container that is used to hold described material.
Technical problem to be solved by this invention can solve the feeding device that a kind of catalytic specie adds in the fuel by a kind of according to the present invention in the described second type waste gas purification apparatus of preface, at this, this material is catalytically-active materials or includes catalytically-active materials or can isolate catalytically-active materials from this material.
Above-mentioned two types waste gas purification apparatus is particularly suitable for implementing first method of the present invention.The advantage of aforementioned this method of enforcement also is applicable to this two kinds of waste gas purification apparatuses similarly.
Described feeding device preferably has a storage container that is used to hold described material.
Six kinds of embodiments and corresponding the inventive method by 1 to 6 pair of apparatus of the present invention of accompanying drawing described in detail below, in the accompanying drawing:
Fig. 1 illustrates first kind of embodiment of waste gas purification apparatus of the present invention;
Fig. 2 illustrates second kind of embodiment of the waste gas purification apparatus of implementing the inventive method;
Fig. 3 illustrates the third embodiment of the waste gas purification apparatus of implementing the inventive method;
Fig. 4 illustrates the 4th kind of embodiment of the waste gas purification apparatus of implementing the inventive method;
Fig. 5 illustrates the 5th kind of embodiment of the waste gas purification apparatus of implementing the inventive method;
Fig. 6 illustrates the 6th kind of embodiment of the waste gas purification apparatus of implementing the inventive method;
Fig. 7 illustrates first kind of measurement result of the method acquisition of adopting second kind of embodiment of the present invention;
Fig. 8 illustrates second kind of measurement result of the method acquisition of adopting second kind of embodiment of the present invention.
Fig. 1 illustrates a pipeline 1, and a reaction chamber 2 is wherein arranged.In this reaction chamber 2, be provided with a catalyst-assembly that comprises three catalyst assemblies 3.A kind of fluid or gas A streamwise 5 flow through this catalyst assembly 3.This gas for example is a kind of waste gas or flue gas.Containing a kind of material or harmful substance in waste gas A, for example is nitrogen oxide NO (NO
x).In order to reduce nitrogen oxide according to SCR (SCR) principle, will be by first feeder sleeve 7 in the feeding pipeline 1 as the ammonia NH (NH of reducing agent
3) be transported among the waste gas A that contains harmful substance NO.Nitrogen oxide NO enters in the catalyst assembly 3 in the reaction chamber 2 together with the ammonia NH that mixs up into.NO changes into nitrogen (N at the there nitrogen oxide
2) and steam (H
2O), make that thus institute's nitrogen-containing oxide reduces strongly from the waste gas stream that this catalyst assembly 3 flows out.
It is the combustion apparatus that fuel comes the power plant of work with combustion gas, oil or coal that described waste gas A for example comes from one.Contained catalytically-active materials K is vanadium, molybdenum, tungsten and/or titanium in the catalyst assembly 3, and their oxide especially.The catalytically-active materials K highly selective that is applied in the SCR method is worked in 300 ℃ to 450 ℃ of preferred temperature range, thereby prevents the side reaction of not expected to a great extent.
The catalytic activity of described catalyst assembly 3 may moved ground, rear section or fully weakened through the long time.Dust or compound may be the reasons that catalytic activity weakens to the effect of described catalytically-active materials K.Compound wherein for example is that institute is halogen-containing among the waste gas A.
For catalyst assembly 3 reactivation in situs that make reduced activity, new or fresh catalytically-active materials KU was imported among the waste gas A before catalyst assembly 3 along the flow direction 5 of waste gas by an injection apparatus 8.This injection apparatus 8 also can for example at first generate this catalytically-active materials KU by this material S with among the another kind of material S input waste gas A and replace input catalytically-active materials KU in waste gas stream A.Catalytically-active materials KU that added or formed is identical with existing in catalyst assembly 3 or original existing catalytically-active materials K, in other words by approximate forming.
Described injection apparatus 8 has a storage container 11 that is used for holding material S or catalytically-active materials KU.Also drawing a feeder sleeve 9 from this storage container 11 in addition feeds in the waste gas A transfer tube 1.This second feeder sleeve 9 is configured in the place that it feeds in the described waste gas transfer tube 1, when making described material S or catalytically-active materials KU in entering pipeline 1 by disperseization or atomizing.
Described pipeline 1, catalyst assembly 3 and first feeder sleeve 7 and described injection apparatus 8 constitute a waste gas purification apparatus 13 together.But this device both fixation application also is applied on the internal combustion engine of vehicle in a combustion apparatus in power plant movably.
Second kind of embodiment of the inventive method shown in Figure 2 has significantly different with first kind of embodiment of front, material S wherein or fresh catalytically-active materials KU at first are mixed among a kind of fuel B, produce waste gas A when this fuel burns in a combustion chamber 15.In this embodiment, described material S or catalytic active substance KU are added among the fuel B in the mode of dissolution mechanism or disperse, and fuel B is sent in the combustion chamber 15 by a cartridge 17 then.In order to carry the fuel B that from a fuel tank 21, extracts, be provided with a pump 19.Material S or catalytically-active materials KU in every kilogram of fuel B shared composition between 10mg and 200mg.
Fuel B burns in combustion chamber 15, forms the waste gas A that contains nitrogen oxide thus.Simultaneously for example in combustion chamber 15, also form described new catalytically-active materials KU by described material S.After flowing out from combustion chamber 15 together with nitrogen oxide NO and new catalytically-active materials KU, waste gas A flows to catalyst assembly 3 in the reaction chamber 2 by pipeline 1.As what in first kind of embodiment, mentioned, in the front of catalyst assembly 3 ammonia NH is mixed up in the air-flow by described first feeder sleeve, 7 streamwises 5.
By be mixed with the fuel B of material S or catalytically-active materials KU one section long time internal combustion, make the catalyst assembly reactivation.
From first measurement result shown in Figure 7, can see this reactivation effect.In this basic experiment, the mixture of a kind of vanadium V and iron Fe is added among the fuel B in a refinery power station as catalytically-active materials KU.Wherein each kilogram fuel B just inserts the vanadium of 102mg and the iron of 252mg.When combustion fuel B, produce the 150000m of common humidity (i.N.feucht)
3The waste gas stream of/h volume flow.Content of vanadium in waste gas A or the flue gas is 316ppm.At this, the basic density of moist flue gas is 1.31kg/m
3The operating temperature of catalyst assembly 3 is 370 ℃.
Be given in (t=0h) when taking fire fuel B in the table below and at the content of vanadium V205 of burning after about 6000 hours (at barium oxide V
2O
5In content), the content of vanadium V205 that records in the inflow side and the outflow side of catalyst assembly 3 respectively just:
| ??t＝0h | ??????????????????????t＝6000h | ||||
| The inflow side | The outflow side | ||||
| Primary importance | The second place | Primary importance | The second place | ||
| ??V205 | ??0.45％ | ??0.93％ | ???1.78％ | ??1.2％ | ??1.31％ |
In the chart of Fig. 7, the axis of ordinates on the left side is represented the degree V205 of vanadium in the catalyst assembly 3, and abscissa is represented time t (unit for hour).
When the reactivation measure begins (t=0h), the content of vanadium V205 in the catalyst assembly 3 of the described loss of activity of part is approximately 0.4%.After through 6000 working hours, utilize RFA (=x-ray fluorescence analysis) to measure the content V205 of vanadium, but the dust of deposition will be removed in advance.
This chart shows, it is about 1.3% that content of vanadium V205 has risen to, and consequently, catalyst assembly 3 is at the catalytic activity K-NO of nitrogen oxide
xAfter through 6000 working hours, bring up to about 48.5m/h (referring to the axis of ordinates on the right) from about 41.5m/h.
In Fig. 8, the axis of ordinates on the right is represented from SO
2Oxidation reaction becomes SO
3Oxygenation efficiency K-SO
xDuration of work at 6000 hours can be observed this oxygenation efficiency and rises to about 550m/h from 200m/h.
The difference of the third embodiment shown in Figure 3 and second kind of embodiment shown in Figure 2 is, described material S or fresh catalytically-active materials KU not at first with fuel tank 21 in fuel B mix, but when from fuel tank 21, taking out fuel B, the described material S of taking-up from an independent container 25 or fresh catalytically-active materials KU are mixed with fuel B.In illustrated embodiment, described material S or catalytically-active materials KU are transported to the cartridge 17 from container 25 by an input pipe 27, thereby mix with fuel B and and then equally with embodiment shown in Figure 2 be transported in the combustion chamber 15 together.This flexible program that fuel B is transported in the combustion chamber 15 also can be realized in embodiment shown in Figure 2.Container 25 and carrier pipe 27 constitute a feeding device 28.
The difference of embodiment shown in Figure 3 and embodiment shown in Figure 2 also is, catalyst assembly 3 is not set.In the present embodiment, the nitrogen oxide NO among the waste gas stream A that produces in when burning only by be mixed among the fuel B catalytically-active materials KU especially in reaction chamber 2 to the effect of nitrogen oxide NO by catalyzed conversion.
The 4th kind of embodiment of the inventive method shown in Figure 4 is used to make a kind of catalyst assembly 3 reactivations to the small part loss of activity.(ex-situ) carries out this reactivation not on the spot in the present embodiment, that is to say under a kind of like this state to carry out reactivation, that is, do not adopting catalyst assembly 3 to come to carry out reactivation under the situation of catalyzed conversion nitrogen oxide NO.Catalyst assembly 3 with described loss of activity is arranged in the reaction chamber 2 for this reason, adopts the material S of the new or fresh catalytically-active materials KU of a kind of conduct then or includes the material S of this catalytically-active materials KU or next wetting this catalyst assembly 3 of material S of the therefrom separable this catalytically-active materials KU of going out.This new catalytically-active materials KU infiltrates in the catalyst substrate 31 thus or deposits on it, and just existing catalytically-active materials K is filled in this substrate 31 or deposits on it when making catalyst assembly 3.Make catalyst assembly 3 reactivations thus.
The 5th kind of embodiment shown in Figure 5 is since one at first on the catalyst substrate 33 of deactivation.This catalyst substrate 33 be subjected to for example burning air-flow that a kind of fuel produced or the impact of waste gas stream A.According to the similar mode (in Fig. 5, not being shown specifically) of Fig. 2 or Fig. 3 otherwise by the pipe tap 29 in the feeding pipeline 1 with a kind of as catalytically-active materials K's or include this catalytically-active materials K's or the therefrom separable this catalytically-active materials K's of going out material S and mix up in the air current A.Therefore, according to embodiment shown in Figure 5, be put in the pipeline 1 that waste gas A flows through by catalyst substrate 33 and produce a catalyst assembly 3 inertia.
The waste gas purification apparatus 41 of the 6th kind of form of implementation shown in Figure 6 is the same with the third form of implementation shown in Figure 3 to comprise a feeding device 28.But with shown in Figure 3 opposite be, in embodiment shown in Figure 6, also the same with embodiment shown in Figure 2 have a catalyst assembly 3 in reaction chamber 2, and it constitutes by a kind of catalytically-active materials K is filled in the catalyst substrate 31 or deposits on it.Therefore, in embodiment shown in Figure 6, catalyst assembly 3 is by the new or fresh catalytically-active materials KU that is added by feeding device 28, or by described catalytic specie S, " on the spot " or " online " reactivation.
Claims (25)
1. method that is used for transforming air-flow (A) material (NO), in particular for the conversion of nitrogen oxides Cheng Shui in the flue gas stream that a kind of and ammonia (NH) is mixed according to the SCR principle and the method for nitrogen, wherein, described air-flow (A) is transported in the reaction chamber (2), described material (NO) is subjected to a kind of catalytically-active materials (K, KU) catalytic action, it is characterized in that, a kind of catalytic specie (S) is transported in the reaction chamber (2) together with air-flow (A), and this material (S) is a kind of catalytically-active materials (K; KU) or can constitute a kind of catalytically-active materials (K by this material (S); KU).
2. the method for claim 1 is characterized in that, described air-flow (A) flows through or flows through one and especially is arranged on catalyst substrate (31 in the reaction chamber (2); 33).
3. method as claimed in claim 2 is characterized in that, described material (S) streamwise (5) is in catalyst substrate (31; 33) preceding being added in the air-flow (A).
4. method as claimed in claim 3 is characterized in that, described material (S) in being added to air-flow (A) time by even dispersion or atomizing.
5. as each described method in the claim 1 to 4, it is characterized in that described material (S) is mixed up in a kind of fuel (B), when this fuel combustion, described material (NO) contained in air-flow (A) produces as waste gas.(referring to Fig. 2,3 and 6)
6. as each described method in the claim 2 to 5, it is characterized in that, in catalyst substrate (31), fill or deposit thereon and go up a kind of catalytically-active materials (K) of facilitating described material (NO) catalyzed conversion, to constitute a catalyst assembly (3).
7. method as claimed in claim 6, it is characterized in that, described catalytically-active materials (KU) and described air-flow (A) together are transfused to or are made of described material (S), and and the catalytically-active materials (K) when making described catalyst assembly (3), having filled or deposited just the same.
8. as each described method in the claim 2 to 5, it is characterized in that,, constitute a catalyst assembly (3) by being filled into the catalytically-active materials (K) in the air-flow (A) in the described catalyst substrate (33) or depositing on it.
9. one kind is used to make a kind of catalyst assembly to the small part loss of catalytic activity (3), especially a kind of method of catalyst assembly (3) reactivation of the nitrogen oxide that is used for reducing a kind of flue gas (A) (NO) according to the work of SCR principle, this catalyst assembly by a kind of catalytically-active materials (K) is deposited among the catalyst substrate (31) or on manufacturedly go out, it is characterized in that, soak this catalyst assembly (3) as material (S) catalytically-active materials (KU) or that include catalytically-active materials (KU) or that can therefrom isolate catalytically-active materials (KU) with a kind of.(with reference to accompanying drawing 1,2,4)
10. method as claimed in claim 9 is characterized in that, the catalytically-active materials (KU) in the described material (S) be filled and/or deposit among the catalytically-active materials (K) that has deposited when making described catalyst assembly and/or on.
11., it is characterized in that catalytically-active materials (KU) in the described material (S) and the catalytically-active materials (K) of having filled or having deposited are just the same as claim 9 or 10 described methods when making described catalyst assembly (3).
12., it is characterized in that described material (S) is transfused to catalyst assembly (3) at the catalyst duration of work as each described method in the claim 9 to 11.
13. method as claimed in claim 12 is characterized in that, described material (S) is facilitated the material (NO) of catalyzed conversion to mix with a kind of catalyst assembly (3) that flows to.
14. as claim 12 or 13 described methods, it is characterized in that described material (S) is mixed up in a kind of fuel (B), when this fuel combustion, produce a kind of material as waste gas (NO), this material (NO) is transported in the described catalyst assembly (3) of facilitating its conversion.
15. as each described method in the claim 1 to 14, it is characterized in that (K contains a kind of element atom in these metallic elements of vanadium, titanium, tungsten, iron and/or molybdenum in KU) to described catalytically-active materials, this catalytically-active materials (K, KU) a kind of especially like this oxide of metal.
16. one kind is used in a combustion process burnt fuel (B), contain a kind of material (S) in this fuel or be added a kind of material (S), this material (S) is catalytically-active materials (KU) or can produces catalytically-active materials (KU) from this material (S) that when burning this fuel (B) is particularly useful for the enforcement of claim 5 or 14 described methods.
17. fuel as claimed in claim 16 (B) is characterized in that, material (S) content in every kilogram of fuel (B) is between 10mg and 200mg.
18., it is characterized in that described material (S) is comprised in the fuel (B) or with dissolution mechanism or disperse mode with dissolution mechanism or disperse mode and is added in the fuel (B) as claim 16 or 17 described fuel (B).
19., it is characterized in that described catalytically-active materials (KU) has the characteristic of facilitating a kind of harmful substance (NO) catalyzed conversion that produces when fuel (B) burns as each described fuel (B) in the claim 16 to 18.
20. as each described fuel (B) in the claim 16 to 19, it is characterized in that described catalytically-active materials (KU) has the characteristic of the nitrogen oxide catalyzed conversion that is contained in the waste gas that fuel (B) burning is produced according to the SCR principle.
21., it is characterized in that described catalytically-active materials (KU) contains at least a in vanadium, titanium, tungsten, iron, the molybdenum or contains the mixture of being made up of them as each described fuel (B) in the claim 16 to 20.
A 22. waste gas purification apparatus (13), in particular for the combustion apparatus in power plant or the waste gas purification apparatus of vehicle internal combustion engine, wherein, the waste gas stream (A) that burning produces flows through a catalyst assembly (3), to transform wherein contained harmful substance (NO), this catalyst assembly (3) be by a kind of catalytically-active materials (K) of facilitating harmful substance (NO) catalyzed conversion is deposited in the catalyst substrate (31) or on manufactured come out, wherein, especially the nitrogen oxide in the waste gas stream (A) can be transformed according to the SCR principle, it is characterized in that a kind of injection apparatus (8), this injection apparatus can infeed a kind of material (S) in the waste gas at waste gas inflow catalyst assembly (3) before along the flow direction (5) of waste gas, at this, this material (S) is catalytically-active materials (KU) or includes catalytically-active materials (KU) or can isolate catalytically-active materials (KU) from this material (S).(with reference to Fig. 1)
23. waste gas purification apparatus as claimed in claim 22 (13) is characterized in that, described injection apparatus (8) has a storage container (11) that is used to be installed in described material (S).
A 24. waste gas purification apparatus (41), in particular for the combustion apparatus in power plant or the waste gas purification apparatus of vehicle internal combustion engine, wherein, the waste gas stream (A) that a kind of combustion fuel (B) produces flows through a catalyst assembly (3), to transform wherein contained harmful substance (NO), this catalyst assembly (3) be by a kind of catalytically-active materials (K) of facilitating this harmful substance (NO) catalyzed conversion is deposited in the catalyst substrate (31) or on and produced, wherein, especially the nitrogen oxide in the waste gas stream (A) can be transformed according to the SCR principle, it is characterized in that a feeding device (43), a kind of material (S) can be added in the fuel (B) by it, at this, this material (S) is catalytically-active materials (KU) or includes catalytically-active materials (KU) or can isolate catalytically-active materials (KU) from this material (S).(referring to Fig. 6)
25. waste gas purification apparatus as claimed in claim 24 is characterized in that, described feeding device (28) has a storage container (45) that is used to be installed in described material (S).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10022763A DE10022763A1 (en) | 2000-05-10 | 2000-05-10 | Catalytically converting nitrogen oxide in exhaust gas stream mixed with ammonia to form water and nitrogen comprises feeding gas stream together with added catalytically active substance to reaction chamber |
| DE10022763.5 | 2000-05-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1429129A true CN1429129A (en) | 2003-07-09 |
| CN1240467C CN1240467C (en) | 2006-02-08 |
Family
ID=7641443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018093124A Expired - Fee Related CN1240467C (en) | 2000-05-10 | 2001-05-10 | Method and device for catalytic conversion of substance |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1296751A1 (en) |
| KR (1) | KR20030015236A (en) |
| CN (1) | CN1240467C (en) |
| DE (1) | DE10022763A1 (en) |
| TW (1) | TW561144B (en) |
| WO (1) | WO2001085311A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285412B (en) * | 2007-04-10 | 2012-05-23 | 通用汽车环球科技运作公司 | Excess NH3 storage control for SCR catalysts |
| CN101233049B (en) * | 2005-07-08 | 2013-05-01 | 法伊利技术公司 | Catalytic reactive component reduction system and methods |
| CN101543793B (en) * | 2008-03-26 | 2015-05-06 | 巴布科克和威尔科克斯能量产生集团公司 | In-situ regeneration of a catalyst masked by calcium sulfate |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7538059B2 (en) * | 2006-01-31 | 2009-05-26 | Rohm And Haas Company | Regeneration of mixed metal oxide catalysts |
| DE102008046381B4 (en) * | 2008-09-09 | 2011-12-22 | Man Truck & Bus Ag | Process for reducing nitrogen oxides in the exhaust gas stream of internal combustion engines |
| FR3043570B1 (en) * | 2015-11-13 | 2020-08-07 | Ifp Energies Now | FLUID FOR DEPOLLUTION OF THERMAL ENGINES AND METHODS OF PREPARATION OF SUCH FLUIDS BY EMULSIFICATION |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3168368A (en) * | 1960-04-27 | 1965-02-02 | Air Prod & Chem | Method of treating exhaust gases of internal combustion engines |
| US5322671A (en) * | 1992-02-25 | 1994-06-21 | Blue Planet Technologies Co., L.P. | Catalytic vessel |
| US5308810A (en) * | 1992-12-28 | 1994-05-03 | Atlantic Richfield Company | Method for treating contaminated catalyst |
| US5519149A (en) * | 1994-10-28 | 1996-05-21 | E. I. Du Pont De Nemours And Company | Vapor phase catalytic oxidation of N-butane to maleic anhydride incorporating in situ catalyst calcination/activation |
| DE19507219C1 (en) * | 1995-03-02 | 1996-05-15 | Daimler Benz Ag | Method and device for post-coating a deactivated catalyst coating on a catalyst |
| AU2253597A (en) * | 1996-01-31 | 1997-08-22 | Clean Diesel Technologies, Inc. | Method and apparatus for reducing harmful emissions from a diesel engine by post combustion catalyst injection |
| DE19800873C2 (en) * | 1998-01-13 | 2000-03-02 | Erc Emissions Reduzierungs Con | Catalyst solution and its use as well as methods for reducing the emission of pollutants in combustion and thermal processes |
| GB2333048B (en) * | 1998-01-13 | 2002-03-20 | Hugh F Collins | A rejuvenating and/or cleaning agent |
| US6395665B2 (en) * | 1998-07-24 | 2002-05-28 | Mitsubishi Heavy Industries, Ltd. | Methods for the regeneration of a denitration catalyst |
-
2000
- 2000-05-10 DE DE10022763A patent/DE10022763A1/en not_active Ceased
-
2001
- 2001-05-09 TW TW090111044A patent/TW561144B/en active
- 2001-05-10 EP EP01940226A patent/EP1296751A1/en not_active Withdrawn
- 2001-05-10 KR KR1020027015010A patent/KR20030015236A/en not_active Application Discontinuation
- 2001-05-10 WO PCT/DE2001/001782 patent/WO2001085311A1/en not_active Application Discontinuation
- 2001-05-10 CN CNB018093124A patent/CN1240467C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101233049B (en) * | 2005-07-08 | 2013-05-01 | 法伊利技术公司 | Catalytic reactive component reduction system and methods |
| CN101285412B (en) * | 2007-04-10 | 2012-05-23 | 通用汽车环球科技运作公司 | Excess NH3 storage control for SCR catalysts |
| CN101543793B (en) * | 2008-03-26 | 2015-05-06 | 巴布科克和威尔科克斯能量产生集团公司 | In-situ regeneration of a catalyst masked by calcium sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001085311A1 (en) | 2001-11-15 |
| EP1296751A1 (en) | 2003-04-02 |
| TW561144B (en) | 2003-11-11 |
| KR20030015236A (en) | 2003-02-20 |
| DE10022763A1 (en) | 2001-11-22 |
| CN1240467C (en) | 2006-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101259377B (en) | Hybrid catalyst for NOx reduction using fuel hydrocarbone as reductant | |
| CN1218420A (en) | Method and apparatus for NOx abatement in lean gaseous streams | |
| US20090205324A1 (en) | Emission control system having a coated mixer for an internal combustion engine and method of use | |
| CN1108862C (en) | Flue gas purifying catalyst | |
| CN1604817A (en) | Process for making metal oxide-coated microporous materials | |
| KR102340327B1 (en) | Catalyst and method for purifying combustion exhaust gas | |
| CN102355934A (en) | Combined waste gas treatment of waste gas streams containing ammonia and nitrogen oxides in industrial plants | |
| CN1123676C (en) | Method for treating by combustino carbon-contg. particles in IC engine exhaust circuit | |
| EP2008713A2 (en) | Nanoalloys in emissions control after-treatment system | |
| CN1318526A (en) | Method for treatment of waste water and device for treatment of waste water using the method | |
| CN1240467C (en) | Method and device for catalytic conversion of substance | |
| CN1182376A (en) | Method of abating Nox and preparation of catalytic material therefor | |
| CN106414983B (en) | With the N in EGR circuit2The exhaust system of O catalyst | |
| CN107261830A (en) | A kind of system and method for ira situ degradation dioxin in flue gas class material | |
| CN110075909A (en) | A kind of purification organic compounds containing nitrogen exhaust gas catalyst | |
| JP2017177060A (en) | Exhaust emission control catalyst | |
| CN113209983A (en) | Cheap and efficient flue gas desulfurization and denitrification catalyst and preparation method thereof | |
| CN1124885C (en) | Method for treating gases to reduce nitrogen oxide emissions using catalytic composition based on silica and titanium oxide | |
| CN101507900B (en) | Device for reducing dibenzo-dioxin and dibenzo-furan emissions from catalytic converters containing transition metals | |
| KR20180041195A (en) | Exhaust gas treatment system and exhaust gas stream treatment method | |
| CN1279150C (en) | Method for increasing working efficiency of diesel fuel combustion treatment system | |
| CN107803218A (en) | Scr catalyst | |
| CN113413909A (en) | Preparation method of catalyst for selective catalytic reduction of NOx in oxygen-enriched environment | |
| CN108071467A (en) | For purifying the device of exhaust gas | |
| JP3395219B2 (en) | Nitrogen oxide removal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |