CN101733146A - Catalyst for synthesizing propylene by using ethylene and butylene - Google Patents
Catalyst for synthesizing propylene by using ethylene and butylene Download PDFInfo
- Publication number
- CN101733146A CN101733146A CN200810043969A CN200810043969A CN101733146A CN 101733146 A CN101733146 A CN 101733146A CN 200810043969 A CN200810043969 A CN 200810043969A CN 200810043969 A CN200810043969 A CN 200810043969A CN 101733146 A CN101733146 A CN 101733146A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- butylene
- mcm
- propylene
- ethene
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for synthesizing propylene by using ethylene and butylene and mainly solves the problems of the prior art that the propylene has low selectivity and the catalyst has short life. The invention adopts a technical scheme that the catalyst for synthesizing the propylene by using the ethylene and the butylene comprises the following compositions in part by weight: a) 1 to 30 parts of tungstic oxide and b) 70 to 99 parts of MCM-22 molecular sieve carrier to well solve the problems. The catalyst can be applied in the industrial production of synthesizing the propylene by using the ethylene and the butylene.
Description
Technical field
The present invention relates to a kind of catalyst that is used for ethene and butylene synthesizing propylene.
Background technology
In recent years, along with the economic constantly development of third world countries, market will constantly increase the demand of light olefin (comprising ethene, propylene etc.).Propylene is that scale is only second to one of most important basic organic of ethene, and its maximum purposes is to produce polypropylene (account for its total amount half), secondly is to produce acrylonitrile, expoxy propane, isopropyl alcohol, isopropylbenzene, oxo-alcohols, acrylic acid, oligomerization of propene thing.
To reach 7,800 ten thousand tons to propylene demand in 2008.Traditional ethene coproduction and refinery reclaim cyclopropene method and obviously are difficult to satisfy growing propylene demand, adopt the olefin(e) disproportionation technology can digest C when not reducing the naphtha pyrolysis severity
4Cut, but and propylene enhancing, thereby preparing propylene through olefin disproportionation Study on Technology and exploitation are not only to improving the output of propylene, simultaneously to promoting low value-added C
4The comprehensive utilization of cut all has great significance, and butylene disproportionation wherein involved in the present invention is produced third and rarely made a kind of up-and-coming technology.
Olefin dismutation reaction is called the olefinic double bonds displacement reaction again, be that a kind of alkene of finding the sixties in 20th century transforms phenomenon, olefin dismutation reaction just becomes the class significant process that alkene transforms since then, utilizes olefin dismutation reaction to be converted into the higher olefin product of multiple added value by the olefin feedstock that some are comparatively cheap, abundant.Can represent the olefin dismutation reaction process with following formula:
Wherein R and R ' represent alkyl or hydrogen atom.The simplest olefin dismutation reaction is that propylene disproportionation generates ethene and butene-2.
US5300718 has reported the route of being produced propylene by the butene-2 raw material that contains butene-1 and oxygenatedchemicals.This technology comprises: at first raw material is passed through the alumina removal oxygenatedchemicals; Butylene isomery under the effect that magnesia is urged turns to butene-2 in the raw material; Butene-2 and ethene disproportionation generate third rare three steps.Wherein the catalyst that uses of butene-2 and ethene disproportionation is MgO and WO
3/ SiO
2Mixed bed.
A kind of technology that obtains the third rare and amylene by butene-1 and butene-2 disproportionation is proposed among the US6271430.This process using tank reactor, catalyst are Re
2O
7/ Al
2O
3, reaction temperature is 0～150 ℃, reaction pressure is 2～200bar.
WO00014038 has introduced a kind of method of preparing propylene by butene disproportionation.The raw material butylene is butene-1, butene-2 or its mixture, and catalyst is WO
3/ SiO
2, common reaction temperature is 500-550 ℃, reaction pressure is 1atm.
US513891 has reported the preparation method of olefin disproportionation catalyst, and its catalyst consists of B
2O
3-Re
2O
7/ Al
2O
3/ SiO
2, as catalyst carrier, the activity of olefin dismutation reaction improves greatly with amorphous aluminum silicide.
EP0152112 has reported with Ti and has modified WO
3/ SiO
2Catalyst carrier; US5905055 has reported with Nb and has modified WO
3/ SiO
2Catalyst carrier, olefin(e) disproportionation activity all obtain to improve.
Catalyst in the above document all exists the propylene selectivity not high when being used for the reaction of ethene and butylene synthesizing propylene, the problem that catalyst life is short.
Summary of the invention
Technical problem to be solved by this invention is to exist product propylene selectivity low in the prior art, and the problem that catalyst life is short provides a kind of new ethene and the catalyst of butylene synthesizing propylene.When this catalyst is used for ethene and butene reaction, has propylene selectivity height, the advantage that catalyst life is long.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for ethene and butylene synthesizing propylene in parts by weight, comprises following component: a) 1～30 part tungsten oxide; B) 70～99 parts MCM-22 molecular sieve carrier.
In the technique scheme, be 5～20 parts in the consumption preferable range of parts by weight tungsten oxide, the specific area of catalyst is 300～800 meters
2/ gram, preferable range is 400～700 meters
2/ gram, more preferably scope is 500～600 meters
2/ gram; The silica alumina ratio Si/Al of MCM-22 molecular sieve is 20～200, and preferable range is 40～120, and more preferably scope is 60～100.
The WO that uses among the present invention
3The preparation method of/MCM-22 molecular sieve catalyst is as follows: sodium aluminate is soluble in water, under stirring condition, add the organic formwork agent hexamethylene imine, and add Ludox (SiO again
225% mass fraction).The material proportion of reactant (mol ratio) is: SiO
2/ Al
2O
3=25～100, OH
-/ SiO
2=0.05～0.3, R/SiO
2=0.08～1.0, H
2O/SiO
2=10～30, stir after 30 minutes, in the reactor of packing into, the crystallization temperature scope in the building-up process is 160～190 ℃, crystallization time is 24～120 hours.Take out, filter, washing, the template agent is removed in roasting, promptly gets MCM-22; With the MCM-22 that the prepares last evaporating dish of putting into of pulverizing, the aqueous solution in tungstenic source is poured into wherein equably, then evaporating dish is placed under the infrared lamp, stir with glass rod and make tungsten ion be uniformly impregnated within the MCM-22 surface; 500～600 ℃ of following roastings 1～8 hour, obtain pale yellow powder; With pressed powder, fragmentation, be sized to the catalyst finished product of required order number.
Among the above-mentioned preparation method, the tungsten source can be a kind of in wolframic acid, sodium tungstate, ammonium tungstate, the ammonium metatungstate, and the tungsten source is an ammonium metatungstate preferably.According to consumption, it is mixed with rare water uses.The system crystallization temperature is preferably in 160～180 ℃; The sintering temperature that MCM-22 removes the template agent is 400～600 ℃, is preferably in 550 ℃, and roasting time was at 4～10 hours, be preferably in 6 hours, heating rate is 1 ℃/minute, and calcination atmosphere is air, oxygen, nitrogen or argon gas, is preferably in air or the oxygen atmosphere.WO
3/ MCM-22 catalyst calcination atmosphere is air, oxygen, nitrogen or argon gas, is preferably in air or the oxygen, and sintering temperature is 500～600 ℃, is preferably in 550 ℃, and roasting time is preferably in 4 hours, and heating rate is 1 ℃/minute; Catalyst after the roasting can be made the particle of all size on demand, and reasonable particle size range is 20～40 orders.
The forming method of catalyst is as follows: with the Ludox that adds 1～10% in the catalyst for preparing, add 0.5～5% field mountain valley with clumps of trees and bamboo powder after stirring a period of time, kneading, drying, roasting make finished product later on.
The catalyst of technique scheme preparation is used for olefin dismutation reaction, and the embodiment of the invention is that butylene and ethene disproportionated reaction generate propylene.Reaction condition is as follows: in the fixed bed reactors, reaction temperature is 0～550 ℃, and reaction pressure is 0～10MPa, and the mass space velocity of butylene is 0.1～10 hour
-1, the mol ratio of ethene and butylene is 1～5: 1.
Butene feedstock can be the mixture of butene-1, butene-2 or butylene in the such scheme, or from the C-4-fraction of steam cracking device.
The present invention is by with the carrier of MCM-22 molecular sieve as catalyst, because the specific area of catalyst is improved, thereby increased WO
3Decentralization, simultaneously the MCM-22 molecular sieve has certain isomerization of butene effect again, so be 300 ℃ in reaction temperature, reaction pressure is 3MPa, the mol ratio of ethene and butylene is 2.5: 1 and 4.8 hours
-1The air speed condition under, with catalyst and ethene, butylene haptoreaction, the selectivity of its propylene can reach 99%, its life-span can reach 300 hours, the life-span is compared WO
3/ SiO
2Catalyst has improved 20%, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
WO
3/ MCM-22's is synthetic
With sodium aluminate (Al
2O
348.6% mass fraction, Na
2O 34.7% mass fraction) 35 grams are dissolved in the 800 gram water, add 200 milliliters of organic formwork agent hexamethylene imines (density 0.88) under stirring condition, add Ludox (SiO again
225% mass fraction) 1200 grams.The material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝30，
OH
-/SiO
2＝0.08，
R/SiO
2＝0.35，
H
2O/SiO
2＝18.5
Stir after 30 minutes, in the reactor of packing into, the crystallization temperature in the building-up process is 160 ℃, and crystallization time is 72 hours.After the taking-up through filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal.
Take by weighing ammonium metatungstate 0.12 gram and put into beaker, add 20 gram deionized waters, pour evaporating dish after the dissolving equably into, and it is placed under the infrared lamp, make tungsten ion be uniformly impregnated within 10 gram MCM-22 surfaces with the glass rod stirring.With the Ludox that adds 5% in the good catalyst for preparing, add 1% field mountain valley with clumps of trees and bamboo powder after stirring a period of time, kneading, drying, roasting make finished product later on, 550 ℃ of following roastings 4 hours, obtain pale yellow powder; With pressed powder, fragmentation, be sized to 20～40 purpose catalyst finished products, the content 1% of tungsten oxide is designated as WMS-1.The evaluation of catalyst is carried out on the olefin(e) disproportionation evaluating apparatus, presses mass fraction and calculates, and the key component of raw material comprises: the normal butane of 38.5% butene-1,24.5% butene-2 and surplus.Reaction is to be 300 ℃ in temperature, and pressure is 3MPa, and the mol ratio of ethene and butylene is 2.5: 1 and 4.8 hours
-1The air speed condition under estimate, evaluation result is as shown in table 2.Life of catalyst is a butene conversion greater than the reaction time of being carried out in 60% o'clock in the table, and conversion ratio is the conversion ratio of butylene, and selectivity is the selectivity of propylene.
[embodiment 2]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 1, only changing ammonium metatungstate is 0.63 gram, and the load capacity of the catalyst oxidation tungsten that makes is 5%, is designated as WMS-2, and its result is as shown in table 2.
[embodiment 3]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 1, only changing ammonium metatungstate is 1.64 grams, and the load capacity of the catalyst oxidation tungsten that makes is 12%, is designated as WMS-3, and its result is as shown in table 2.
[embodiment 4]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 1, only changing ammonium metatungstate is 3.01 grams, and the load capacity of the catalyst oxidation tungsten that makes is 20%, is designated as WMS-4, and its result is as shown in table 2.
[embodiment 5]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 1, only changing ammonium metatungstate is 5.16 grams, and the load capacity of the catalyst oxidation tungsten that makes is 30%, is designated as WMS-5, and its result is as shown in table 2.
[embodiment 6]
WO
3/ MCM-22's is synthetic
With sodium aluminate (Al
2O
348.6% mass fraction, Na
2O 34.7% mass fraction) 35 grams are dissolved in the 800 gram water, add 200 milliliters of organic formwork agent hexamethylene imines (density 0.88) under stirring condition, add Ludox (SiO again
225% mass fraction) 1200 grams.The material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝10，
OH
-/SiO
2＝0.08，
R/SiO
2＝0.35，
H
2O/SiO
2＝18.5
Stir after 30 minutes, in the reactor of packing into, the crystallization temperature in the building-up process is 160 ℃, and crystallization time is 72 hours.After the taking-up through filtration, washing, drying.It is MCM-22 that X-ray diffractometer records the gained crystal, and the mole silica alumina ratio of MCM-22 is 20.
Take by weighing ammonium metatungstate 1.64 grams and put into beaker, add 20 gram deionized waters, pour evaporating dish after the dissolving equably into, and it is placed under the infrared lamp, make tungsten ion be uniformly impregnated within 10 gram MCM-22 surfaces with the glass rod stirring.With the Ludox that adds 5% in the good catalyst for preparing, add 1% field mountain valley with clumps of trees and bamboo powder after stirring a period of time, kneading, drying, roasting make finished product later on, 550 ℃ of following roastings 4 hours, obtain pale yellow powder; With pressed powder, fragmentation, be sized to 20～40 purpose catalyst finished products, the content 12% of tungsten oxide is designated as WMS-6.The evaluation of catalyst is carried out on the olefin(e) disproportionation evaluating apparatus, and reaction condition is as shown in table 3 with embodiment 1 evaluation result.
[embodiment 7]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 6, only change SiO
2/ Al
2O
3Be 20, the catalyst that makes is designated as WMS-7, and evaluation result is as shown in table 3.
[embodiment 8]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 6, only change SiO
2/ Al
2O
3Be 50, the catalyst that makes is designated as WMS-8, and evaluation result is as shown in table 3.
[embodiment 9]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 6, only change SiO
2/ Al
2O
3Be 80, the catalyst that makes is designated as WMS-9, and evaluation result is as shown in table 3.
[embodiment 10]
WO
3/ MCM-22's is synthetic
Press each step and operating condition among the embodiment 6, only change SiO
2/ Al
2O
3Be 100, the catalyst that makes is designated as WMS-10, and evaluation result is as shown in table 3.
[embodiment 11]
The roasting of synthetic sample
Get the sample WMS-1 of above-mentioned drying, WMS-2, WMS-3, WMS-4, WMS-5 placed tube furnace, with gas space velocity 1000 hours
-1Bubbling air rises to 550 ℃ with 1 ℃/minute heating rate by room temperature, and under the condition that feeds nitrogen, 550 ℃ kept 4 hours.
Sample after the roasting carries out low temperature N
2The absorption test, measurement result is as follows:
Table 1WO
3The BET analysis result of/MCM-22 sample
[comparative example 1]
Immersion process for preparing WO
3/ SiO
2Sample
Take by weighing 20 gram silica gel samples (15 order), its specific surface is 350 meters
2/ gram, SiO
2Content is 99.9%, and other takes by weighing ammonium metatungstate 2.72 grams, adds 30 milliliters of deionized waters, under agitation is added drop-wise to respectively in the silica gel sample, leaves standstill and dries, and 120 ℃ of oven dry 4 hours, places 550 ℃ of following roastings of Muffle furnace 6 hours, obtains sample 12%WO
3/ SiO
2Be designated as BJS, its evaluation result is shown in table 2,3.
Table 2 different loads amount WO
3The evaluation result of/MCM-22 sample
As can be known from Table 2, comparative sample BJS inactivation when reaction proceeds to 280 hours, the conversion ratio of butylene has only 55.9%, and WO
3The butene conversion of/MCM-22 sample can obtain the WO of different loads amount all greater than 60%
3/ MCM-22 catalyst has the longer life-span, and all has higher butene conversion and propylene selectivity in course of reaction.
Table 3 Different Silicon aluminum ratio WO
3The evaluation result of/MCM-22 sample
As can be known from Table 3, comparative sample BJS inactivation when reaction proceeds to 260 hours, the conversion ratio of butylene has only 57.8%, and WO
3The butene conversion of/MCM-22 sample can obtain the WO of Different Silicon aluminum ratio all greater than 60%
3/ MCM-22 catalyst has the longer life-span, and all has higher butene conversion and propylene selectivity in course of reaction.
Claims (8)
1. a catalyst that is used for ethene and butylene synthesizing propylene in parts by weight, comprises following component: a) 1～30 part tungsten oxide; B) 70～99 parts MCM-22 molecular sieve carrier.
2. the catalyst that is used for ethene and butylene synthesizing propylene according to claim 1 is characterized in that the consumption in the parts by weight tungsten oxide is 5～20 parts.
3. the catalyst that is used for ethene and butylene synthesizing propylene according to claim 1, the specific area that it is characterized in that catalyst is 300～800 meters
2/ gram.
4. the catalyst that is used for ethene and butylene synthesizing propylene according to claim 3, the specific area that it is characterized in that catalyst is 400～700 meters
2/ gram.
5. the catalyst that is used for ethene and butylene synthesizing propylene according to claim 4, the specific area that it is characterized in that catalyst is 500～600 meters
2/ gram.
6. the catalyst that is used for ethene and butylene synthesizing propylene according to claim 1, the silica alumina ratio Si/Al that it is characterized in that the MCM-22 molecular sieve is 20～200.
7. the catalyst that is used for ethene and butylene synthesizing propylene according to claim 6, the silica alumina ratio Si/Al that it is characterized in that the MCM-22 molecular sieve is 40～120.
8. the catalyst that is used for ethene and butylene synthesizing propylene according to claim 7, the silica alumina ratio Si/Al that it is characterized in that the MCM-22 molecular sieve is 60～100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810043969A CN101733146B (en) | 2008-11-21 | 2008-11-21 | Catalyst for synthesizing propylene by using ethylene and butylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810043969A CN101733146B (en) | 2008-11-21 | 2008-11-21 | Catalyst for synthesizing propylene by using ethylene and butylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101733146A true CN101733146A (en) | 2010-06-16 |
| CN101733146B CN101733146B (en) | 2012-09-05 |
Family
ID=42457476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810043969A Active CN101733146B (en) | 2008-11-21 | 2008-11-21 | Catalyst for synthesizing propylene by using ethylene and butylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101733146B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739431A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Method of preparing propylene from ethylene and butylene |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160155C (en) * | 1999-04-28 | 2004-08-04 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing arylhydrocarbon with mathane and its application in synthesizing reaction |
| CN1120047C (en) * | 2001-02-28 | 2003-09-03 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dismutation reaction and its preparing process and application |
| CN1559683A (en) * | 2004-03-04 | 2005-01-05 | 厦门大学 | Preparing aromatics loading catalyst by methane at non oxidation catalyzing aromatization |
| CN100363259C (en) * | 2004-12-23 | 2008-01-23 | 中国科学院大连化学物理研究所 | Method for preparing MCM-22 molecular sieve in high silicon |
| CN100443175C (en) * | 2005-08-15 | 2008-12-17 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through olefin disproportionation |
-
2008
- 2008-11-21 CN CN200810043969A patent/CN101733146B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739431A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Method of preparing propylene from ethylene and butylene |
| CN103739431B (en) * | 2012-10-17 | 2016-04-13 | 中国石油化工股份有限公司 | For the method for ethene and butylene propylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101733146B (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101279287B (en) | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis | |
| CN101468318B (en) | Modified rare-earth-containing molecular sieve catalyst as well as preparation method and use thereof | |
| CN107265478B (en) | A kind of boron modification ferrierite molecular sieve catalyst and the preparation method and application thereof | |
| CN102452878A (en) | Method for preparing low-carbon olefin by synthetic gas one-step technology | |
| CN103012034A (en) | Method for removing micro-quantity alkene in aromatic hydrocarbon | |
| CN103071523A (en) | Lanthanum-phosphorus double-heteroatom ZSM-5 molecular sieve catalyst and preparation method thereof | |
| CN102040444B (en) | Method for preparing propylene by butylene and ethene | |
| CN101768040B (en) | Method for preparing propylene from butylene and ethylene | |
| CN102372572B (en) | Method for preparing propylene through C4 disproportionation | |
| CN101992119B (en) | Catalyst for preparing propylene from butane and ethylene and preparation method thereof | |
| CN101602639A (en) | Produce the method for ethylene, propylene | |
| CN101733146B (en) | Catalyst for synthesizing propylene by using ethylene and butylene | |
| CN102039150A (en) | Preparation method of binderless Y zeolite catalyst | |
| CN104549295B (en) | Olefin isomerization catalyst | |
| CN101172925B (en) | Method for producing propylene with dismutation of ethylene and butylene | |
| CN105582933A (en) | Catalyst used for double-bond isomerization | |
| CN102583433A (en) | Modified silicon-boron molecular sieve, and preparation method and application thereof | |
| CN102872900A (en) | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene | |
| CN102372537A (en) | Method for preparing propylene and aromatic hydrocarbon through methanol conversion | |
| CN102875316B (en) | Method for preparing ethylbenzene by alkylation of dry gas and benzene | |
| CN104275193B (en) | metathesis catalyst | |
| CN104549351B (en) | Isomerization catalyst | |
| CN101347745B (en) | Catalyst for producing ethylene and propylene by catalytic pyrolysis of naphtha | |
| CN100531910C (en) | Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene | |
| CN103739431B (en) | For the method for ethene and butylene propylene |
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 |