CN1078492C - Dense-phase circulating fluidized bed reactor for strong exothermal reaction process - Google Patents
Dense-phase circulating fluidized bed reactor for strong exothermal reaction process Download PDFInfo
- Publication number
- CN1078492C CN1078492C CN98119380A CN98119380A CN1078492C CN 1078492 C CN1078492 C CN 1078492C CN 98119380 A CN98119380 A CN 98119380A CN 98119380 A CN98119380 A CN 98119380A CN 1078492 C CN1078492 C CN 1078492C
- Authority
- CN
- China
- Prior art keywords
- bed
- reactor
- reaction
- reaction process
- phase
- 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.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 239000012071 phase Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims description 17
- 239000007790 solid phase Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 16
- 230000004087 circulation Effects 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract 1
- 238000010574 gas phase reaction Methods 0.000 abstract 1
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000012808 vapor phase Substances 0.000 description 7
- 235000010215 titanium dioxide Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002826 coolant Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000476 thermogenic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The present invention relates to a dense-phase circulation fluidized-bed reactor for a strong heat-discharging reaction process. A main bed of the reactor is composed of an upper part and a lower part, wherein the upper part is an expanding section, and the lower part is the main bed and an accompanying bed; the main bed is connected with the accompanying bed by a connecting pipe; the upper part of the expanding section is provided with a cyclone separator, and the lower part is provided with a cooling wind distributor; the lower part of the main bed and the lower part of the accompanying bed are both provided with air distributors; the upper part of the accompanying bed has an inlet of a solid-phase reaction object, and the lower part has a cooling wind inlet. The reactor of the present invention is suitable for a strong hot gas-phase reaction process or a two phases of gas and solid reaction process. The present invention can realize the effective control of a reaction temperature and a reaction rate in the reaction process.
Description
The present invention relates to a kind of strong exothermal reaction process dense-phase circulating fluidized bed reactor that is used for, belong to technical field of chemical.
Existing rapid circulating fluidized bed reactor, its structural principle as shown in Figure 1, among Fig. 1, the 1st, reactor, the 2nd, cyclone separator, the 3rd, fast gas-solid separation device, the 4th, regenerator, the 5th, riser reactor, the 6th, the secondary wind inlet, 7 is wind inlets, the 8th, the regeneration wind inlet.This structure is in the energy, the existing application widely of field of petrochemical industry, and typical commercial Application process has catalytic pyrolysis, fluid cracking, acrylonitrile synthetic [Wei Fei etc., petrochemical industry, 27 (1998) 4, pp.276-280] etc.The rapid circulating fluidized bed operating gas velocity is much larger than the operating gas velocity of turbulent fluidized bed, and solid particle and the reaction gas flow time of staying in bed is shorter.In addition, bed density is less, and general bed solid holdup is lower than 10%.Thereby the rapid circulating fluidized bed reactor is only applicable to some specific reaction system.Usually, such reactor is applied to catalyst rapid deactivation and reaction speed gas phase catalytic reaction process faster more.But the rapid circulating fluidized bed reactor can not satisfy the technological requirement of strong heat release gas-solid course of reaction.
The objective of the invention is to design a kind of strong exothermal reaction process dense-phase circulating fluidized bed reactor that is used for, the circulation in a large number in reactor by catalyst or introducing inert particle, realization is to the reaction rate of catalysis or on-catalytic gas-solid strong exothermal reaction process and effective control of reaction temperature, avoid reaction temperature fluctuation and " temperature runaway " phenomenon, solve a series of problems such as reactor selection, anticorrosion, explosion-proof and product stability.
What the present invention designed is to be used for the strong exothermal reaction process dense-phase circulating fluidized bed reactor, its reactor is made up of upper and lower two parts, top is expanding reach, the bottom is main bed and companion's bed, links to each other by tube connector in the lower end between main bed and the companion's bed, and the top of expanding reach is provided with cyclone separator, the bottom is provided with the cooling air distributor, the bottom of main bed and companion's bed is equipped with gas distributor, and the top of companion's bed is the solid-phase reactant inlet, and the bottom is a cooling air inlet.Cooling air distributor in its expanding reach is made up of inside and outside two endless tubes, and this endless tube communicates with cooling air inlet, is distributed with the qi-emitting hole pipe on the endless tube.
The present invention design be used for the strong exothermal reaction process dense-phase circulating fluidized bed reactor, novel reactor is operated in bubbling or turbulence fluidisation area, operating gas velocity generally is lower than 0.5 meter per second; Bed density is bigger, and the bed solid holdup is generally more than 40%.The circulation in a large number in reactor by catalyst or introducing inert particle, realization is to the reaction rate of catalysis or on-catalytic gas-solid strong exothermal reaction process and effective control of reaction temperature, avoid reaction temperature fluctuation and " temperature runaway " phenomenon, solved a series of problems such as reactor selection, anticorrosion, explosion-proof and product stability well.Reactor of the present invention is applicable to strong heat release gas phase or gas-solid two phase reaction process, can realize the effective control to the reaction temperature and the reaction rate of course of reaction, thereby can satisfy reaction temperature, the higher technical process of reaction rate stability requirement.
Description of drawings:
Fig. 1 is the prior art structural representation.
Fig. 2 is the structural representation of the reactor that designs of the present invention.
Fig. 3 is one embodiment of the present of invention.
Fig. 4 is the A-A cutaway view of Fig. 3.
Fig. 5 is the B-B cutaway view of Fig. 3.
Below in conjunction with accompanying drawing, introduce content of the present invention in detail.
Among Fig. 2～Fig. 5, the 11st, main bed, the 12nd, companion's bed, the 13rd, gas distributor, the 14th, expanding reach, the 15th, cooling air distributor, the 16th, cyclone separator, 17 is wind inlets, the 18th, secondary wind inlet, the 19th, companion's bed wind inlet, the 20th, cooling air inlet, the 21st, product outlet, the 22nd, the solid-phase reactant inlet, the 23rd, the connector between main bed and the companion's bed, the 24th, cold wind distributor endless tube, the 25th, qi-emitting hole pipe.
As shown in Figure 2, the main bed 11 of its reactor is made up of upper and lower two parts, top is expanding reach 14, the bottom is main bed 11 and companion's bed 12, has tube connector 23 to link to each other between main bed and the companion's bed, and the top of expanding reach is provided with cyclone separator 16, the bottom is provided with cooling air distributor 15, the bottom of main bed and companion's bed all is provided with gas distributor 13, and the top of companion's bed is solid-phase reactant inlet 22, and the bottom is a cooling air inlet 19.Cooling air distributor in its expanding reach is made up of inside and outside two endless tubes 24, and this endless tube communicates with cooling air inlet 20, is distributed with qi-emitting hole pipe 25 on the endless tube.
The operation principle of the reactor of the present invention's design is as follows:
Fluidisation is carried out by vapor-phase reactant and small amounts of inert gas in main bed zone 11 in the reactor, and in bubbling or the operation of turbulence fluidisation area.Because bed expansion in fluid mapper process, bed density reduces, and the bed pressure drop that makes main bed zone is less than companion's bed 12 zones.Main bed 11 forms huge particle circulation driving force with this pressure differential between companion's bed 12, thereby the particle in the reactor can be led between bed and the companion's bed and realizes that high speed circulates.The high speed circulation of solid particle, one side can be improved the mixed characteristic of bed; Also can make system temperature in whole reactor, be tending towards homogeneous on the other hand, effectively control the hot(test)-spot temperature of reactor.
In the operating process, solid-phase reactant adds from the charging aperture 22 on companion bed top, carries out premixed in circulation folding process and inert particle, enter main bed mixed zone after because the violent turbulence of fluidized state makes it further mixed even.By regulating the ratio of solid phase particles and inert particle, can control the concentration of the solid-phase reactant that enters reaction zone.Meet and chemical reaction takes place at reaction zone solid-phase reactant and vapor-phase reactant.Course of reaction liberated heat and fluidized particles carry out heat exchange.Because the volumetric heat capacity of solid particle is much larger than the volumetric heat capacity of gas, exothermic heat of reaction is curbed to the thermogenic action of system.By a large amount of circulations of solid particle, in time the chemical reaction liberated heat is shifted out reaction zone, thereby control the temperature rising amplitude of reaction zone effectively.Inert particle after reaction zone is heated intensification is recycled the heat transfer zone that rises to the top, carries out direct or indirect heat exchange with cooling medium, and the inert particle after being cooled enters companion's bed race way and carries out next circulation.And vapor-phase reactant mainly enters main bed from wind inlet 17, and whether 18 view volumes systems of secondary wind need to add the inertia fluidizing agent and decide, and as need inertia fluidizing agent, then the inertia fluidizing agent adds with the form of secondary wind and becomes owner of bed; Otherwise secondary wind inlet also should be introduced vapor-phase reactant.
Suitably the flow-rate ratio of wind of adjusting and secondary wind cooperates the adjusting to companion's bed wind, can realize the quantitative control to the solid particle cycle rate, 30000 kilograms/meter of control ranges
2Second is to 200000 kilograms/meter
2Second.By introducing inertia fluidizing agent, the concentration that can dilute vapor-phase reactant, thereby also be one of technical measures of slowing down strong heat exchange fast reaction severe degree.The gaseous product that obtains of reaction rises and passes heat transfer zone, with after solid particle separates, draws reactor through cyclone separator 16 from exporting 21 through reactor top expanding reach 16 again.
Establish expanding reach 14 at main bed and companion's bed top, both made things convenient for and in expanding reach, settled the heat exchange device,, be beneficial to gas solid separation again, reduce carrying secretly of airflow convection particle as cooling air distributor 15.Therefore, after one-level or two utmost point cyclonic separation dedustings, the dust content of gas-phase product is very low, can satisfy the requirement of most of technical process when adopting the present invention to design.
In the expanding reach heat transfer zone, can adopt gas-solid fluidized direct heat transfer or through interior displacer indirect heat exchange dual mode according to technological requirement.The former is applicable to that cooling medium needs heat temperature raising, and can with the process of further handling again after product is directly mixed; The latter is applicable to that then product does not allow the situation of mixing with cooling medium.After the heat transfer zone heat exchange, make the temperature of ciculation fluidized particle be reduced to the technological requirement value.Reaction heat be used for heating up medium to be heated or produce middle and high pressure steam, steam can be used as dried feed, product and heats the thermal source of other material, also can be used for generating.Therefore, novel reactor of the present invention both can effectively have been controlled the reaction temperature and the reaction rate of course of reaction, also can make full use of reaction heat energy effectively.
Another characteristics of novel dense-phase circulating fluidized bed reactor are that control is flexible, and operating flexibility is big.Bulk temperature is controlled by inlet temperature and the inlet flow rate of regulating cooling medium in the reaction system, and the reaction zone temperature rise is by the cycle rate control of fluidized particles.Control to the product generating rate realizes by the adding speed of regulating solid-phase reactant, the adding speed of adjusting vapor-phase reactant or the dual control of employing gas-solid two phase reaction thing feed rate.Because a large amount of circulations of solid particle make dense-phase circulating fluidized bed reactor have good cushioning effect,, also can obtain more stable product generating rate substantially at reactor outlet even the reinforced process of certain reactant fluctuates to some extent.
Introduce embodiments of the invention below.
Embodiment 1 novel dense-phase circulating fluidized bed reactor is applied to chloride process titanium dioxide powder production process as the alchlor generator, can obtain good effect.Alchlor is as the nucleation initator of titanium dioxide building-up process and crystal agent transition, requires the product quality height, generating rate is stable and a large amount of reaction heat are used to heat titanium white synthesis material TiCl
4The solid-phase reactant aluminium powder adds reactor with basicly stable speed, accurately controls the form adding of the feed rate of vapor-phase reactant with a wind, inert gas TiCl
4(titanium dioxide synthesis material) adds with the form of secondary wind and becomes owner of bed and add heat transfer zone with the direct cool cycles fluidisation of fluidized forms particle as cooling medium.Course of reaction is controlled under 530 ℃ of temperature carries out, and the reaction zone temperature rise is less than 10 ℃, all titanium dioxide synthesis material TiCl
4Can be heated up more than 80 ℃.This process can obtain highly stable alchlor generating rate, alchlor that is generated and TiCl
4Evenly be mixed into synthetic titanium dioxide oxidation furnace.
Embodiment 2 novel dense-phase circulating fluidized bed reactors are applied to by rice husk production high quality white carbon black (SiO
2) process.By the burning carbon process of the white carbon black of rice husk production, very high to the requirement of reaction temperature, in case reaction temperature transfinites,, can not get qualified product even product and impurity react and can not remove.Utilize the temperature control characteristic of novel dense-phase circulating fluidized bed reactor of the present invention, the temperature of burning the carbon process can be controlled at ± 20 ℃ more among a small circle in.Thereby can guarantee the quality of product, reduce the cost of production process.Utilize and burn carbon reaction heat production high steam, part is used for the drying of raw material and product, and remainder can be used for generating.
Claims (2)
1, a kind of strong exothermal reaction process dense-phase circulating fluidized bed reactor that is used for, it is characterized in that, this reactor is made up of upper and lower two parts, and top is expanding reach, and the bottom is main bed and companion's bed, link to each other by tube connector in the lower end between main bed and the companion's bed, the top of expanding reach is provided with cyclone separator, and the bottom is provided with the cooling air distributor, and the bottom of main bed and companion's bed is equipped with gas distributor, the top of companion's bed is the solid-phase reactant inlet, and the bottom is a cooling air inlet.
2, reactor as claimed in claim 1 is characterized in that, the cooling air distributor in the wherein said expanding reach is made up of inside and outside two endless tubes, and this endless tube communicates with cooling air inlet, is distributed with the qi-emitting hole pipe on the endless tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98119380A CN1078492C (en) | 1998-09-25 | 1998-09-25 | Dense-phase circulating fluidized bed reactor for strong exothermal reaction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98119380A CN1078492C (en) | 1998-09-25 | 1998-09-25 | Dense-phase circulating fluidized bed reactor for strong exothermal reaction process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1214959A CN1214959A (en) | 1999-04-28 |
| CN1078492C true CN1078492C (en) | 2002-01-30 |
Family
ID=5226360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98119380A Expired - Fee Related CN1078492C (en) | 1998-09-25 | 1998-09-25 | Dense-phase circulating fluidized bed reactor for strong exothermal reaction process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1078492C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721961B (en) * | 2008-10-29 | 2012-01-25 | 中国石油化工股份有限公司 | Fluidized bed reactor |
| CN101721960B (en) * | 2008-10-29 | 2012-02-29 | 中国石油化工股份有限公司 | Fluidized bed reactor |
| CN101721962B (en) * | 2008-10-29 | 2012-04-04 | 中国石油化工股份有限公司 | Three-phase fluidized bed reactor |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618305B (en) * | 2008-07-04 | 2012-05-30 | 中国石油化工股份有限公司 | Fluidized bed reactor |
| CN102039106B (en) * | 2009-10-21 | 2012-09-12 | 中国石油化工股份有限公司 | Novel fluidized bed reactor |
| CN105642196A (en) * | 2015-12-31 | 2016-06-08 | 天津市职业大学 | Visual fluidized bed reactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4232633A (en) * | 1977-05-09 | 1980-11-11 | Chambert Lars A A | Process and reactor for conducting exothermal reactions in a circulating fluidized bed |
| CN85108854A (en) * | 1984-12-07 | 1986-05-10 | 法国精炼公司 | Improved fluid charge catalytic cracking of hydrocarbon oils device and processing method |
-
1998
- 1998-09-25 CN CN98119380A patent/CN1078492C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4232633A (en) * | 1977-05-09 | 1980-11-11 | Chambert Lars A A | Process and reactor for conducting exothermal reactions in a circulating fluidized bed |
| CN85108854A (en) * | 1984-12-07 | 1986-05-10 | 法国精炼公司 | Improved fluid charge catalytic cracking of hydrocarbon oils device and processing method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721961B (en) * | 2008-10-29 | 2012-01-25 | 中国石油化工股份有限公司 | Fluidized bed reactor |
| CN101721960B (en) * | 2008-10-29 | 2012-02-29 | 中国石油化工股份有限公司 | Fluidized bed reactor |
| CN101721962B (en) * | 2008-10-29 | 2012-04-04 | 中国石油化工股份有限公司 | Three-phase fluidized bed reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1214959A (en) | 1999-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kunii et al. | Fluidization engineering | |
| US2536099A (en) | Means for forming stages in fluidized masses | |
| US3672069A (en) | Fluidized-bed cooler and method of cooling particulate solid material | |
| US4152407A (en) | Process and apparatus for exothermic reactions | |
| CN106622044A (en) | Ammonia oxidation reactor and preparation method of nitrile compounds | |
| US5120691A (en) | Process for regulating or checking the thermal level of a pulverulent solid incorporating a heat exchanger with fluidized bed compartments | |
| RU2156651C2 (en) | Fluidized-bed reactor and method of performing chemical reactions therein | |
| CN101804314A (en) | Fluidized bed reactor | |
| US4881592A (en) | Heat exchanger with backmix and flow through particle cooling | |
| CN1958146B (en) | Multiple stage fluidized-bed reactor and method for synthesizing chloroethylene | |
| CN1078492C (en) | Dense-phase circulating fluidized bed reactor for strong exothermal reaction process | |
| EP1549687B1 (en) | Polymerization process | |
| WO1990013772A1 (en) | Fluidized bed reactor using capped dual-sided contact units and method for use | |
| CN104190330A (en) | Jet flow fluidized bed reaction device and olefin polymerization method thereof | |
| CN2339296Y (en) | Close-phase circulation fluidizing-bed reactor for strong heat-discharging reaction process | |
| US5027893A (en) | Heat exchanger with backmix and flow-through particle cooling | |
| CN107249728A (en) | Method and synthesis reactor for implementing chemical synthesis | |
| US3208831A (en) | Apparatus for storing and stripping catalyst in a fluidized system | |
| Kelkar et al. | Development of fluidized catalytic reactors: Screening and scale‐up | |
| WO1988004199A1 (en) | Fluidized bed | |
| CN108479640A (en) | A kind of gas distributor and the system containing the distributor | |
| JPH045487B2 (en) | ||
| US3473887A (en) | Aluminum fluoride production | |
| US4536380A (en) | Process for conducting reactions using a circulating magnetically stabilized bed to control reaction temperature profile | |
| US2699988A (en) | Apparatus for synthesis of organic compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| 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 |