CN1102848A - An antifoulant for petrochemical processes - Google Patents
An antifoulant for petrochemical processes Download PDFInfo
- Publication number
- CN1102848A CN1102848A CN94107845A CN94107845A CN1102848A CN 1102848 A CN1102848 A CN 1102848A CN 94107845 A CN94107845 A CN 94107845A CN 94107845 A CN94107845 A CN 94107845A CN 1102848 A CN1102848 A CN 1102848A
- Authority
- CN
- China
- Prior art keywords
- petroleum chemistry
- scale inhibitor
- dirt
- give birth
- prevents
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
This invention relates to an antifoulant for petrochemical processes comprising a hydrogen-donating hydroaromatic compound is disclosed. It can be handled easily, is inexpensive, has no adverse effect on the process, shows excellent effect to prevent formation of fouling, and enables continuous operation of a plant for a long time with good stability.
Description
The present invention relates to a kind of novel scale inhibitor that is used for petroleum chemistry processing.Be particularly related to a kind of scale inhibitor that is used for petroleum chemistry processing, this scale inhibitor can prevent in the technological process of petrochemical factory effectively such as generate dirt in the treating process of ethylene production factory.
Petrochemical plant such as ethylene production factory in, the fluid that contains alkene such as ethene and propylene and diolefins such as divinyl is distilled, in such fluidic still-process, this fluid must be with heat modification in addition, form sludge by heat, for example in preheat exchanger or reboiler, and the sludge that forms so just sticks on the heat-transfer surface of preheat exchanger or reboiler; Perhaps adhere on the surface of pipeline and form dirt.
The mechanism that forms as dirt has following known phenomenon:
In petrochemical process, organic compound in working fluid is easy to oxidation such as the compound as alkene and diolefins in the unsaturated hydrocarbons, these compounds cause the generation of hydroperoxide in working fluid owing to dissolved oxygen, these hydroperoxide are decomposes then, particularly form ketone, aldehyde, carboxylic acid etc. in the presence of material such as the metal that the band catalytic activity is arranged, these compounds are aggregated and form oligopolymer and polymkeric substance sludge.
Therefore, use antioxidant such as phenol antioxidant and amine antioxidants, polymerization retarder such as oximes inhibitor and nitroso-group inhibitor, prevent to form sludge and throw out agglutinating dispersion agent and the medicament that is used in combination with these medicaments in petrochemical process as scale inhibitor, its purpose just is to prevent aforesaid dirt.For example: (1) by aniline and tert-butyl catechol in conjunction with and the scale inhibitor formed [Japan speciallys permit communique, clear and 59(1984)-24138; ] (2) scale inhibitor of forming by nitrosophenol [Japan's special permission is open, put down into 3(1991)-350147]; (3) scale inhibitor be made up of aminated compounds of the scale inhibitor of being made up of nitroso compound [Japanese specail comment communique is put down into 4(1992)-26639] and (4) [Japan's special permission is open, clear and 64(1989)-13041] all disclosed already.
Yet because these scale inhibitors directly are added in the operating process, their shortcoming is: make product painted; Form unfavorable by product; And then they are difficult for handling; These scale inhibitors; Its antiscaling effect is insufficient, thereby, one segment length's time of operate continuously such as 2 years or the longer time in go wrong.
As mentioned above, scale inhibitor commonly used is often unsatisfactory, and therefore, people wish to develop a kind of scale inhibitor that is used for petroleum chemistry processing strongly, and this scale inhibitor is easy to handle; Cheaply; Technological process there is not retroaction; Preventing that dirt from forming and have the chromatic effect of going out and can one segment length's time of operate continuously under good stability.
The object of the invention is: a kind of scale inhibitor that is used for petroleum chemistry processing is provided, this scale inhibitor overcomes the shortcoming of the habitual scale inhibitor that is used for petroleum chemistry processing, be easy to handle, cheaply, for course of processing low-disturbance, preventing that dirt from demonstrating chromatic effect on forming, can make equipment one segment length's time of operate continuously under good stability.
The inventor has in development on the scale inhibitor that is used for petroleum chemistry processing of above-mentioned premium properties and has done extensive and deep research.Like that, find that the object of the invention can award the hydrogen hydroaromatic compound and reach by containing shown in this result of study, the present invention is accomplished on this finds.
Therefore, the invention provides a kind of scale inhibitor of awarding hydrogen hydrogen aromatic substance that contains that is used for petroleum chemistry processing.
The present invention also provides a kind of method that prevents to generate dirt in petroleum chemistry equipment, and this method comprises: the above-mentioned scale inhibitor that is used for petroleum chemistry processing is added to the working fluid that is supplied to the petrochemical process of giving birth to dirt.
Other purposes of the present invention, characteristic and advantage will be clear more fully in the following description.
As mentioned above, the formation of dirt be in working fluid by radical chain reaction by due to the oxidation of the unsaturated hydrocarbons of alkene and diolefins.The hydrogen hydroaromatic compound of awarding as scale inhibitor has following function in the present invention: make chain reaction end and prevent from effectively to give birth to dirt by the group that produces is granted proton in oxidation.Comprise as the example of awarding the hydrogen hydroaromatic compound: 1,2,3,4 ,-tetraline, 9,10-dihydro phenanthrene, 1,2,3,4,5,6,7,8-eight phenanthrene and hydrogenated terphenyl, these compounds can use separately or two or more compound combines use.
In scale inhibitor of the present invention, except that the hydrogenation aromatic hydrocarbon, also can use conventional scale inhibitor as required, such as: the antioxidant as amine antioxidants and phenols oxidation inhibitor, poly-inhibitor, metal deactivator and the various dispersion agent of containing as oximes inhibitor and nitroso-group inhibitor.Dispersion agent is scattered in organic sludge and inorganic sludge in the process fluid, and prevents that throw out is bonded on heat transmitter or the pipeline surface.Dispersion agent comprises:
(1) having molecular weight is about 1000 to 10000 poly-alkyl (methyl) acrylate and by the mixture of the represented polyethylene polyamine cycloalkanoimide of following general formula:
Wherein, R
1Hydrocarbyl group, n that representative has 10 to 15 carbon atoms represent 1 to 5 integer, and preferably 1 to 3, m represents 1 to 10 integer, and is best 1 to 3, and the weight ratio of each compound is in 90: 10 to 10: 90 scopes in the mixture;
(2) by the represented succinimide derivatives of one of following general formula:
Wherein, R
2It is 400 to 3000 polybutene group that expression has nucleidic mass, R
3Expression has 1 to 5 carbon atom, is preferably the imine group of 1 to 3 carbon atom, R
4And R
5Expression is respectively for hydrogen atom or have that carbon atom is 1 to 5, the groups of best 1 to 3 carbon atom, and P represents 1 to 10 integer.
(3) by the phosphorothioate derivative of following general formula representative or its ethylene oxide adduct:
Wherein, R
6Be that to have nucleidic mass be 500 to 2000 polybutene group; And
(4) having nucleidic mass is 10,000 to 1,000,000 vinylbenzene and maleate copolymer, and it represents general formula as follows:
Wherein, R
7And R
8Each representative has the straight or branched alkyl or the alkenyl of 12 to 18 carbon atoms, and q and r represents digital, two kinds of unitary mol ratios of this numeral (q: r) in 1: 9 to 9: 1 scope, can use two kinds or two or more dispersion agents as required.
The example that is used for poly-alkyl (methyl) acrylate of above-mentioned dispersion agent (1) comprises having the alkyl that carbonatoms is 5 to 18 alkyl (methyl) Voncoat R 3310, the multipolymer that co-polymerization by two or more said alkyl (methyl) acrylate obtains, and the multipolymer that obtains with the co-polymerization of unsaturated monomer such as N-vinyl-2 pyrrolidone of one or more insatiable hunger key and diethylaminoethyl-(methyl) acrylate by one or more said alkyl (methyl) acrylate with alkene.
The amount of the various components in scale inhibitor is used as required, and such as antioxidant, polymeric inhibitor, metal deactivator and dispersion agent are not limited especially, as long as suitably selected.The working fluid that adds scale inhibitor of the present invention is not limited especially yet, and scale inhibitor of the present invention can be added in the pending oil of any kind of, in this oil, forms dirt when handling in petroleum chemistry processing.Scale inhibitor of the present invention preferably puts in the work oil of handling in preheat exchanger or the reboiler in distillation tower, in the depropanizer on ethylene unit, deethanizer, debutanizer or condensation stripping tower.
Below the best approach example that applies scale inhibitor of the present invention is described.The annexing ingredient of awarding hydrogen hydroaromatic compound and other component such as other scale inhibitor and use in addition as required is dissolved in the appropriate solvent, has concentration about 0.5 to 60(weight so that be mixed with) solution of %.The solution of so preparation is made an addition in the device of formation dirt in petroleum chemistry processing, such as heat exchanger, reboiler or pipeline continuously; Perhaps be added in the raw material oil groove to a full dose.The addition of scale inhibitor of the present invention in working fluid generally selected according to the scope of 0.5 to 50000 milligram every liter of amount of working fluid, best 30 to 200 milligrams.
Because scale inhibitor of the present invention has the outstanding performance of antiscale, therefore make equipment one segment length's time of operate continuously under good stability become possibility such as 2 years to 3 years, compare only three months power lifetime of the latter with conventional scale inhibitor.The result can expect energy-conservation and lower maintenance cost, and then can prevent to be accompanied by the caused shut-down of accident.
It is as follows to sum up advantage of the present invention: the scale inhibitor that is used for petroleum chemistry processing is easy to handle, cheaply, to course of processing low-disturbance, preventing to form the outstanding effect of demonstration on the dirt, make equipment operate continuously one segment length under good stability the time become possibility, and energy-conservation and reduction maintenance cost.
Will be with reference to the following example to the present invention's easy to understand more, however these embodiment are used to set forth the present invention and can not be considered to limit the scope of the invention.
Embodiment 1 to 6 and comparative example 1 are as follows to 4:
The medicament that is shown in various types of and each quantity of table 1 is added in the depropanizer bottom flow of taking from a just on-stream device, this mixture is poured in 200 milliliters of autoclaves of the stainless steel of SUS304, handled 20 hours down at 100 ℃, under reduced pressure distill this processed fluid then, obtain residue on evaporation amount (amount of polymers of formation) after the drying.The inhibiting rate that dirt forms is according to above-mentioned income value the ratio that derives from the analog value that does not contain above-mentioned medicament to be calculated, and is used for evaluating its anti-scaling property.
In table 1, used dispersion agent is that to have nucleidic mass be 15000 vinylbenzene and the multipolymer of maleic acid ester and the tert-butyl catechol of representing with TBC.
Comparative example 1 and 2 shows good result on the inhibiting rate that dirt forms, yet in fact contraposition one nitro-0-cresols can not use, because it has problem on handling.
Claims (11)
1, the scale inhibitor that is used for petroleum chemistry processing contains and awards the hydrogen hydroaromatic compound.
2, according to the said scale inhibitor that is used for petroleum chemistry processing of claim 1, wherein, awarding the hydrogen hydroaromatic compound is a kind of compound that is selected from following one group of compound: 1,2,3,4 ,-tetraline, 9,10-dihydro phenanthrene, 1,2,3,4,5,6,7,8-octahydro phenanthrene and hydrogenated terphenyl.
3, according to the said scale inhibitor that is used for petroleum chemistry processing of claim 1, wherein, said scale inhibitor contains the dispersion agent that disperses sludge to use.
4, according to the said scale inhibitor that is used for petroleum chemistry processing of claim 3, wherein, the dispersion agent used of said dispersion sludge is selected from a kind of in following one group of compound at least: poly-alkyl (methyl) acrylate and mixture, succinamide derivative, phosphorothioate derivative or its ethylene oxide adduct of polyethylene polyamine cycloalkanoimide and the multipolymer of vinylbenzene and maleic acid ester.
5, prevent from the petroleum chemistry device, to give birth to the method for dirt, among the working fluid that the said scale inhibitor of claim 1 is added to the petrochemical process that is supplied to living dirt.
6, according to the said method that prevents from the petroleum chemistry device to give birth to dirt of claim 5, wherein, the scale inhibitor that will be used for petroleum chemistry processing is added among the working fluid with the amount of 0.5 to 50,000 mg/litre scope.
7, according to the said method that prevents to give birth to dirt in the petroleum chemistry device of claim 5, wherein, the scale inhibitor that will be used for petroleum chemistry processing made an addition among the working fluid before the device that forms dirt enters petroleum chemistry equipment continuously.
8, according to the said method that prevents to give birth to dirt in petroleum chemistry equipment of claim 5, wherein, the scale inhibitor that will be used for petroleum chemistry processing makes an addition to the raw material tank of the working fluid of petroleum chemistry equipment.
9, according to the said method that prevents to give birth to dirt in petroleum chemistry equipment of claim 5, wherein, said petroleum chemistry equipment is ethylene plant.
10, according to the said method that prevents to give birth to dirt in petroleum chemistry equipment of claim 5, wherein, said scale inhibitor contains the dispersion agent that is useful on the dispersion sludge.
11, according to the said method that prevents from petroleum chemistry equipment, to give birth to dirt of claim 10, wherein, said being used for disperses the dispersion agent of sludge to be selected from a kind of of following one group of medicament at least: poly-alkyl (methyl) acrylate and mixture, succinamide derivative, phosphorothioate derivative or its ethylene oxide adduct of polyethylene polyamine naphthenic acid acid amides and the multipolymer of vinylbenzene and maleic acid ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP189249/1993 | 1993-07-01 | ||
| JP5189249A JPH0718265A (en) | 1993-07-01 | 1993-07-01 | Antifouling agent for petrochemical process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1102848A true CN1102848A (en) | 1995-05-24 |
| CN1110534C CN1110534C (en) | 2003-06-04 |
Family
ID=16238133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94107845A Expired - Fee Related CN1110534C (en) | 1993-07-01 | 1994-07-01 | An antifoulant for petrochemical processes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0632121B1 (en) |
| JP (1) | JPH0718265A (en) |
| KR (1) | KR0140052B1 (en) |
| CN (1) | CN1110534C (en) |
| BR (1) | BR9402609A (en) |
| DE (1) | DE69423140T2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452786A (en) * | 2019-08-07 | 2019-11-15 | 南京汇达化工有限公司 | Add hydrogen antiscale agent prescription and its production method |
| CN114729270A (en) * | 2019-11-27 | 2022-07-08 | 埃科莱布美国股份有限公司 | Antifouling compositions for crude oil production and processing |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007106926A (en) * | 2005-10-14 | 2007-04-26 | Hakuto Co Ltd | Stain adhesion-preventing agent for petroleum refining and method of preventing stain of petroleum-refining plant |
| US9200213B2 (en) | 2008-03-24 | 2015-12-01 | Baker Hughes Incorporated | Method for reducing acids in crude or refined hydrocarbons |
| JP5562348B2 (en) | 2009-11-04 | 2014-07-30 | 株式会社日立ハイテクノロジーズ | Opening device and automatic analyzer using the same |
| EP2581421A1 (en) | 2011-10-12 | 2013-04-17 | Ineos Europe AG | Additive |
| CA3034383A1 (en) | 2016-08-25 | 2018-03-01 | General Electric Company | Reduced fouling of hydrocarbon oil |
| JP2020509126A (en) * | 2017-02-27 | 2020-03-26 | エコラブ ユーエスエイ インク | Antifoulant formulations for compressors |
| JP6485598B1 (en) * | 2017-05-09 | 2019-03-20 | 株式会社片山化学工業研究所 | Methods for preventing contamination of heat exchangers in petroleum processes. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1246481A (en) * | 1984-03-20 | 1988-12-13 | Frank Souhrada | Coking residuum in the presence of hydrogen donor |
| CA1291057C (en) * | 1986-12-19 | 1991-10-22 | Junichi Kubo | Method for hydrocracking heavy fraction oils |
| US5215649A (en) * | 1990-05-02 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for upgrading steam cracker tars |
| US5139643A (en) * | 1991-03-13 | 1992-08-18 | Betz Laboratories, Inc. | Phosphorus derivatives of polyalkenylsuccinimides and methods of use thereof |
| EP0576982A1 (en) * | 1992-06-30 | 1994-01-05 | Nippon Oil Co. Ltd. | Process for converting heavy hydrocarbon oil into light hydrocarbon fuel |
-
1993
- 1993-07-01 JP JP5189249A patent/JPH0718265A/en active Pending
-
1994
- 1994-06-28 DE DE69423140T patent/DE69423140T2/en not_active Expired - Fee Related
- 1994-06-28 EP EP94109954A patent/EP0632121B1/en not_active Expired - Lifetime
- 1994-06-30 KR KR1019940015379A patent/KR0140052B1/en not_active IP Right Cessation
- 1994-06-30 BR BR9402609A patent/BR9402609A/en not_active Application Discontinuation
- 1994-07-01 CN CN94107845A patent/CN1110534C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452786A (en) * | 2019-08-07 | 2019-11-15 | 南京汇达化工有限公司 | Add hydrogen antiscale agent prescription and its production method |
| CN114729270A (en) * | 2019-11-27 | 2022-07-08 | 埃科莱布美国股份有限公司 | Antifouling compositions for crude oil production and processing |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0632121B1 (en) | 2000-03-01 |
| JPH0718265A (en) | 1995-01-20 |
| CN1110534C (en) | 2003-06-04 |
| EP0632121A2 (en) | 1995-01-04 |
| EP0632121A3 (en) | 1995-05-17 |
| BR9402609A (en) | 1995-04-04 |
| DE69423140T2 (en) | 2000-08-24 |
| KR0140052B1 (en) | 1998-06-15 |
| KR950003422A (en) | 1995-02-16 |
| DE69423140D1 (en) | 2000-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1110534C (en) | An antifoulant for petrochemical processes | |
| US5468367A (en) | Antifoulant for inorganic fouling | |
| JPH09132789A (en) | Hydroxyl-substituted monolactone useful as intermediate for preparing lubricating oil additive and fuel additive | |
| US4061545A (en) | Polymerization inhibitor for vinyl aromatic compounds | |
| JPH09137014A (en) | Method for preparing composition useful as intermediate for preparing lube oil additive and fuel additive | |
| AU760809B2 (en) | Styrene monomer polymerization inhibition using substituted dihydroxyarenes and nitroxides | |
| CN101646699A (en) | Improved antifoulant for hydrocarbon processing equipment | |
| CN107987888B (en) | High-temperature-resistant high-vacuum scale inhibitor for oil refining equipment | |
| EP1127040A1 (en) | Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons | |
| US4090946A (en) | Method of stabilizing mineral oil and its refinery products | |
| US6797021B2 (en) | Process of preparation of novel mannich bases from hydrogenated and distilled cashew nut shell liquid (CNSL) for use as additive in liquid hydrocarbon fuels | |
| US3390073A (en) | Hydrocarbon additive for heatexchanger anti-fouling | |
| US3772182A (en) | Antifouling compositions and processes for using them | |
| US4132603A (en) | Polymerization inhibitor for vinyl aromatic compounds | |
| US20230120367A1 (en) | Antifouling agents for plastic-derived synthetic feedstocks | |
| US3585123A (en) | Acylated hydrocarbon succinates and uses thereof | |
| CA2063293A1 (en) | Methods and compositions for inhibiting polymerization of vinyl monomers | |
| EP1897908B1 (en) | Antifoulant dispersant composition and method of use | |
| US5240469A (en) | Antifoulant composition comprising an acrylate ester containing C4 -C22 alcohol esters and amino alcohol esters and phenylene diamine | |
| US5332491A (en) | Iron sulfide dispersing agents | |
| US10604431B2 (en) | Method to disperse byproducts formed in dilution steam systems | |
| US5427690A (en) | α-olefin/maleic anhydride copolymers as antifoulants in quench water systems | |
| CN113563927A (en) | Efficient and environment-friendly scale inhibitor for gasoline stripping tower of ethylene device and preparation method of scale inhibitor | |
| CA2894242A1 (en) | Olefin-acrylate polymers in refinery and oilfield applications | |
| US5783109A (en) | Dispersion of gums and iron sulfide in hydrocarbon streams with alkyl phenol-polyethylenepolyamine formaldehyde resins |
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 |