CN101992107B - Method for preparing catalyst for alkane ammonia oxidation reaction - Google Patents
Method for preparing catalyst for alkane ammonia oxidation reaction Download PDFInfo
- Publication number
- CN101992107B CN101992107B CN2009100577997A CN200910057799A CN101992107B CN 101992107 B CN101992107 B CN 101992107B CN 2009100577997 A CN2009100577997 A CN 2009100577997A CN 200910057799 A CN200910057799 A CN 200910057799A CN 101992107 B CN101992107 B CN 101992107B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- gram
- solution
- preparation
- dissolved
- 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.)
- Active
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a catalyst for alkane ammonia oxidation reaction, which mainly solves the problems that the catalyst is formed nonuniformly, Te is volatile, the preparation technology is complex, the preparation environment is unstable, and active ingredients of the catalyst are volatile so as to cause low stability of the catalyst. A Mo-V-Nb-Te or Sb base is taken as a main component of the catalyst, and the catalyst comprises a silicon dioxide carrier and a composition with a general formula of MoVaNbbCcDdOx in an atomic ratio, wherein C is at least one of Te or Sb, and D is one of Sn, Ti, Fe, Bi, Al or W. A spray drying method is adopted, and the problems are solved by a technical scheme that a reducing agent is added in the preparation process to change the preparation environment, namely corresponding salt or oxides of Mo, Te or Sb are dissolved, solution of corresponding salt or oxides of V and Nb is respectively added, a needed amount of reducing agent is added to regulate an oxidation state, and a needed amount of silica sol is added for performing spray drying. The method can be applied to industrial production of preparing unsaturated nitriles by alkane ammonia oxidation.
Description
Technical field
The present invention relates to a kind of preparation method of alkane ammoxidation reaction catalyst.Especially about a kind of propane ammoxidation acrylonitrile production or iso-butane prepared by ammoxidation methacrylonitrile Preparation of catalysts method.
Background technology
Manage the ammoxidation of propylene technology of the most of BP/Sohio of employing of production of present acrylonitrile; But along with going deep into of petrochemical industry change of market and the research of alkane selective oxidation; Because propane and the price difference XOR iso-butane of propylene and the price variance of isobutene, come into one's own day by day by the process route of propane ammoxidation acrylonitrile production or iso-butane prepared by ammoxidation methacrylonitrile.
For obtaining the propane ammoxidation acrylonitrile production catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.Previously attempt to develop a kind of propane ammoxidation is generated the effective ways of acrylonitrile, the result is that yield is not high enough, perhaps in the charging thing, must add halogen and make co-catalyst.In the charging thing, must add halogen and do in the co-catalyst method, not only require reactor to process, and require the co-catalyst quantitative recovery by extraordinary resistant material.This surcharge has been offset the advantage of propane/propylene price difference, has hindered these catalyst in industrial application.
Patent CN1029397C discloses certain O composite metallic oxide catalyst that contains V, Sb, W and some optional elements, is applied in C
3～C
4Alkane ammoxidation is produced α; The method of alpha, beta-unsaturated nitriles and alkene, wherein the average valence mumber of Sb be higher than+3, the average valence mumber of V is lower than+5; The method is used in propane ammoxidation when producing acrylonitrile; In the reactant steam need be arranged, severe reaction conditions is brought influence to later industrialized plant capacity.
Patent CN1062306A discloses the catalyst system of alkane ammoxidation; Adopt a kind of granulate mixture of two kinds of catalyst components; First kind of catalyst component is effective especially to quickening by alkane generation unsaturated nitrile and alkene; Second kind of catalyst component is effective especially to the conversion of unsaturated nitrile to quickening alkene, and the method system is complicated, and acrylonitrile yield is lower.
Patent CN1178903C discloses the vanadium-antimony-oxide substrate catalyst that the molybdenum that is used for selective paraffin ammoxidation helps catalysis; With the catalyst after the moistening equably calcining of the aqueous solution that contains molybdenum, drying is washed with isobutanol after the calcining again; The method prepares the process complicacy; In the preparation process, wash with isobutanol, and then dry, operate dangerous property.
Patent CN1087734C discloses a kind of method that is prepared acrylonitrile or methacrylonitrile by propane or iso-butane through ammoxidation; Catalyst comprises that composite oxides and load above that have the silica supports of composite oxides, and wherein composite oxides are expressed as:
Mo
1Te
aV
bNb
cX
dO
n
Wherein X is at least a element that is selected from tantalum, tungsten, chromium, titanium, zirconium, antimony, bismuth, tin, hafnium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, zinc, aluminium, gallium, indium, thallium, phosphorus and alkaline-earth metal.
Above-mentioned catalyst can obtain higher acrylonitrile yield, but contains volatile element Te in the catalyst activity component, need in reaction, add Te, and stability is bad, thereby does not have enough life-spans to make this method uneconomical.
Patent CN1174801C discloses a kind of formula Mo that contains
1V
aNb
bX
cZ
yQ
fO
n, wherein X is at least a element that is selected from Te and Sb; Y is at least a element that is selected from Al and W; Z is at least a element that is selected from the element that can be individually formed the oxide with rutile structure, and has the source use of the Z oxide of rutile structure as the Z of preparation catalyst; Q is at least a element that is selected from titanium, tin, germanium, lead, tantalum, ruthenium, rhenium, rhodium, iridium, platinum, chromium, manganese, technetium, osmium, iron, arsenic, cerium, cobalt, magnesium, nickel and zinc; And the Q compound that does not have rutile structure uses as the source of the Q of preparation catalyst.The catalyst acrylonitrile yield that this method makes is higher, but forms complicatedly, and the ingredient requirement height makes that commercial production repeatability is bad and seems uneconomical.
Patent CN1771085A discloses a kind of catalytic gas phase oxidation of propane or iso-butane or oxide catalyst of gas phase catalysis ammoxidation of being used for; It comprises with the specific atoms ratio and contains molybdenum (Mo), vanadium (V), niobium (Nb) and antimony (Sb) as the oxide of component, uses H
2O
2The percent reduction and the specific area of methods such as the oxidation state control catalyst of adjustment oxide.The catalyst that this method makes can stably be produced unsaturated carboxylic acid or unsaturated nitrile with higher yields for a long time, but the controlled condition harshness makes Catalyst Production be difficult for.
All exist corresponding salt of Sb or oxide to reflux among the existing preparation method, adopt the V of severe toxicity
2O
5Be raw material, or the catalyst activity component that makes is volatile and cause problems such as catalyst stability is bad, directly causes preparation process of preparing environment unstable at last, makes that corresponding unsaturated nitrile yield is not high or catalyst stability is bad and seem uneconomical.
The present invention alkane ammoxidation system α different from the past, the place of alpha, beta-unsaturated nitriles Preparation of catalysts method is: 1. catalyst is formed simply, and raw material is easy to get; 2. Preparation of Catalyst good reproducibility, forming degree is good, and the catalyst yield that makes is high, has good stability, and reaction temperature is low, can be used in the commercial production.
Summary of the invention
Technical problem to be solved by this invention is to overcome all to exist Sb backflow to cause complicated process of preparation and yield not high in the prior art document; Te is volatile to cause problems such as catalyst stability is bad, and a kind of preparation method of alkane ammoxidation reaction catalyst is provided.This shaping of catalyst degree is good, has advantages of excellent oxidation-reduction stability, and reaction temperature is low, and product cleans and can keep for a long time the advantage of higher yields.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of alkane ammoxidation reaction catalyst, contain silica supports and comprise the composition of following general formula with atomic ratio measuring:
MoV
aNb
bC
cD
dO
x
Wherein, C is selected from least a among Te or the Sb, and D is selected from a kind of among Sn, Ti, Fe, Bi, Al or the W;
The span of a is 0.1～1.0;
The span of b is 0.01～1.0;
The span of c is 0.01～1.0;
The span of d is 0～1.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst;
This Preparation of catalysts comprises the steps:
1) with aequum Mo and Te or corresponding salt of Sb or the oxide solution (I) of processing soluble in water;
2) with corresponding salt of aequum V or the oxide solution (II) of processing soluble in water;
3) with corresponding salt of aequum Nb or the oxide solution (III) of processing soluble in water;
4) with corresponding salt of aequum D or the oxide solution (IV) of processing soluble in water;
5) aequum is selected from the reducing agent solution (V) of processing soluble in water of oxalic acid, hydrazine hydrate, tartaric acid, pyruvic alcohol;
6) solution (II) is joined in the solution (I); Successively solution (III), solution (IV) and solution (V) are joined wherein again; The Ludox that adds aequum at last; Make the slurry of catalyst, this slurry stirred be evaporated to behind the required solid content spray-drying under 200～400 ℃ of inlet temperatures, temperature be in 400～800 ℃ the inert atmosphere roasting 0.5～8 hour the alkane ammoxidation catalyst.
In the technique scheme; Reducing agent is preferably at least a or its mixture in oxalic acid and the pyruvic alcohol; Slurry solid content preferable range is 25～50% before the spray-drying, and spray-drying inlet temperature preferable range is 250～380 ℃, and catalyst sintering temperature preferable range is 500～700 ℃; Calcination atmosphere is preferably nitrogen, and the roasting time preferable range is 1～4 hour.
The raw material of preparation catalyst of the present invention is:
The most handy corresponding oxide of molybdenum component in the catalyst or its ammonium salt; The most handy corresponding oxide of vanadium component or its ammonium salt; The most handy corresponding oxide of tellurium component, hydroxide or its ammonium salt in the catalyst, the most handy corresponding oxide of antimony component, hydroxide or its ammonium salt; Niobium can be used its oxide, hydroxide, nitrate or oxalates.
For reaching above-mentioned purpose and advantage; Method of the present invention also is included in gas phase makes the alkane that is selected from propane and iso-butane and molecular oxygen and ammonia carry out catalytic reaction, and wherein reactant reacts at reaction zone and catalyst, preparation α; Alpha, beta-unsaturated nitriles, acrylonitrile or methacrylonitrile; Desired molecule oxygen can be used pure oxygen from technical standpoint in the raw material components, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Getting into the ammonia of fixed bed reactors and the mol ratio of propane is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propane is 8～16, is preferably 9.0～14.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fixing bed bioreactor, reaction temperature was 370～450 ℃, was preferably 390～430 ℃.
Though catalyst of the present invention is formed simple; But owing to improved the Preparation of catalysts method; Adopt spray drying process; In the preparation process, regulate the oxidation state of oxide, thereby make that generating crystal between Te or Sb, the Mo obtains good catalyst stability, the catalyst that availability can be good through adding reducing agent.Preparation method's good reproducibility of the present invention, the catalyst that makes are used for propane ammoxidation reaction acrylonitrile yield up to 37%, and forming degree is good; The stability test result was good in 720 hours; Acrylonitrile yield also remains on more than 34%, and reaction temperature is low to moderate 400 ℃, has obtained better technical effect.
Activity of such catalysts of the present invention examination is in internal diameter is 8 millimeters fixed bed reactors, to carry out.Loaded catalyst 2.0 gram, 400 ℃ of reaction temperatures, reaction pressure are normal pressure, proportioning raw materials (mole) is a propane: ammonia: air=1: 1.2: 10, catalyst time of contact is 1.2 gram-second/milliliters.
The definition of conversion of propane, acrylonitrile selectivity and once through yield is following in the present invention:
Below by embodiment the present invention is further elaborated, but the present invention is not limited by following examples.
The specific embodiment
[embodiment 1]
72.1 gram ammonium heptamolybdates and 23.6 gram telluric acids are dissolved in the 300.0 gram hot water, process solution (I); 16.2 gram ammonium metavanadates are dissolved in the 333.0 gram hot water, process solution (II); 30.6 gram niobium oxalates are dissolved in the 85.0 gram hot water, process solution (III); 11.6 gram oxalic acid are dissolved in 20.0 grams process solution (IV) in the water.Under agitation solution (I) is joined in the solution (II); Add solution (III) and solution (IV) more successively, add 250 gram weight concentration at last and be 40% Ludox, make the slurry of catalyst; It is 33% that this slurry stirring is evaporated to solid content; Be 350 ℃ of following spray-dryings in inlet temperature then, roasting is 2 hours in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst 50%Mo
1V
0.34Nb
0.24Te
0.25O
x+ 50%SiO
2, get 20～40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[comparative example 1]
14.4 gram ammonium heptamolybdates and 4.72 gram telluric acids are dissolved in the 40.0 gram hot water, process solution (I); 3.24 gram ammonium metavanadates are dissolved in the 70.0 gram hot water, process solution (II); 6.12 gram niobium oxalates are dissolved in the 17.0 gram hot water, process solution (III).Under agitation solution (I) is joined in the solution (II), add solution (III) again, add 50 gram weight concentration at last and be 40% Ludox; Make the slurry of catalyst; This slurry is stirred evaporation down at 90 ℃ obtain viscous paste always, dry then, grind; Roasting is 2 hours in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst 50%Mo
1V
0.34Nb
0.24Te
0.25O
x+ 50%SiO
2, get 20～40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[embodiment 2～6 and comparative example 2～3]
Adopt the catalyst that has different compositions in the following table with embodiment 1 essentially identical method preparation, and under following reaction condition, carry out the reaction of propane ammoxidation generation acrylonitrile, specifically change and the results are shown in Table 1 with prepared catalyst.
The reaction condition of the foregoing description and comparative example is:
Internal diameter is 8 millimeters fixed bed reactors
400 ℃ of reaction temperatures
The reaction pressure atmospheric pressure
Loaded catalyst 2.0 grams
Catalyst gram-second/milliliter times of contact 1.2
Proportioning raw materials (mole) propane/ammonia/air=1/1.2/10
Table 1
| Embodiment | Catalyst is formed | The preparation committed step | Conversion of propane % | Acrylonitrile selectivity % |
| Embodiment 1 | 50％Mo 1V 0.34Nb 0.24Te 0.25O x+50％SiO 2 | Spray-drying, solid content are 33%, and reducing agent is an oxalic acid | 62.5 | 59.8 |
| Comparative example 1 | 50％Mo 1V 0.34Nb 0.24Te 0.25O x+50％SiO 2 | No spray-drying, no reducing agent | 41.5 | 30.4 |
| Comparative example 2 | 60％Mo 1V 0.31Nb 0.22Te 0.01O x+40％SiO 2 | Reducing agent is an oxalic acid, roasting in the air | 7.7 | 8.6 |
| Comparative example 3 | 20％Mo 1V 1.1Nb 0.11Sb 0.23O x+80％SiO 2 | Spray-drying, no reducing agent, roasting in the air | 7.5 | 5.3 |
| Embodiment 2 | 50％Mo 1V 0.42Nb 0.22Te 0.23O x+50％SiO 2 | Spray-drying, solid content are 45%, and reducing agent is a pyruvic alcohol | 58.9 | 57.6 |
| Embodiment 3 | 40％Mo 1V 0.31Nb 0.22Sb 0.23Bi 0.01O x +60％SiO 2 | Roasting is 4 hours in 500 ℃ of nitrogen | 58.2 | 55.9 |
| Embodiment 4 | 70％Mo 1V 0.31Nb 0.21Sb 0.17O x+30％SiO 2 | Spray-drying, 320 ℃ of inlet temperatures, reducing agent is an oxalic acid | 58.8 | 54.3 |
| Embodiment 5 | 40％Mo 1V 0.31Nb 0.22Sb 0.23Bi 0.01Mg 0.02O x +60％SiO 2 | Spray-drying, solid content are 33%, and reducing agent is an oxalic acid | 62.8 | 60.7 |
| Embodiment 6 | 60％Mo 1V 0.31Nb 0.22Te 0.17W 0.02O x +40％SiO 2 | Roasting is 4 hours in 700 ℃ of nitrogen | 57.2 | 53.5 |
| Embodiment 7 | 50％Mo 1V 0.34Nb 0.24Te 0.25O x+50％SiO 2 | Spray-drying, reducing agent are oxalic acid, and successive reaction is after 720 hours | 60.6 | 56.9 |
The stable appraisal result of embodiment 1 and comparative example 1 is seen table 2
Table 2
Claims (1)
1. the preparation method of an alkane ammoxidation reaction catalyst comprises the steps:
72.1 gram ammonium heptamolybdates and 23.6 gram telluric acids are dissolved in the 300.0 gram hot water, process solution (I);
16.2 gram ammonium metavanadates are dissolved in the 333.0 gram hot water, process solution (II);
30.6 gram niobium oxalates are dissolved in the 85.0 gram hot water, process solution (III);
11.6 gram oxalic acid are dissolved in 20.0 grams process solution (IV) in the water;
Under agitation solution (I) is joined in the solution (II), add solution (III) and solution (IV) more successively, add 250 gram weight concentration at last and be 40% Ludox, make the slurry of catalyst; It is 33% that this slurry stirring is evaporated to solid content, is 350 ℃ of following spray-dryings in inlet temperature then; Roasting is 2 hours in 600 ℃ of nitrogen atmospheres, can get the propane ammoxidation catalyst, and wherein the content of silica is 50% by weight percentage, Mo
1V
0.34Nb
0.24Te
0.25O
xContent be 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100577997A CN101992107B (en) | 2009-08-31 | 2009-08-31 | Method for preparing catalyst for alkane ammonia oxidation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100577997A CN101992107B (en) | 2009-08-31 | 2009-08-31 | Method for preparing catalyst for alkane ammonia oxidation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101992107A CN101992107A (en) | 2011-03-30 |
| CN101992107B true CN101992107B (en) | 2012-08-01 |
Family
ID=43783148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100577997A Active CN101992107B (en) | 2009-08-31 | 2009-08-31 | Method for preparing catalyst for alkane ammonia oxidation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101992107B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549224B (en) * | 2013-10-28 | 2017-09-15 | 中国石油化工股份有限公司 | Unsaturated nitrile catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390642A (en) * | 2001-05-23 | 2003-01-15 | 罗姆和哈斯公司 | Mixed metal oxide catalyst and preparation thereof |
| CN1454711A (en) * | 2002-05-01 | 2003-11-12 | 罗姆和哈斯公司 | Loading type mixed metal oxide catalyst |
| CN101306376A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Tellurium containing alkane ammoxidation reaction catalyst |
| CN101428230A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalysts for the ammoxidation of alkanes |
-
2009
- 2009-08-31 CN CN2009100577997A patent/CN101992107B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390642A (en) * | 2001-05-23 | 2003-01-15 | 罗姆和哈斯公司 | Mixed metal oxide catalyst and preparation thereof |
| CN1454711A (en) * | 2002-05-01 | 2003-11-12 | 罗姆和哈斯公司 | Loading type mixed metal oxide catalyst |
| CN101306376A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Tellurium containing alkane ammoxidation reaction catalyst |
| CN101428230A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalysts for the ammoxidation of alkanes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101992107A (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101306376B (en) | Tellurium containing alkane ammoxidation reaction catalyst | |
| TWI579044B (en) | High efficiency ammoxidation process and mixed metal oxide catalysts | |
| CN101797510B (en) | Catalyst containing rare earth for ammoxidation of alkane | |
| EP2550098B1 (en) | Attrition resistant mixed metal oxide ammoxidation catalysts | |
| EP2550099B1 (en) | Process for preparing improved mixed metal oxide ammoxidation catalysts | |
| US8153546B2 (en) | Mixed metal oxide ammoxidation catalysts | |
| TWI655029B (en) | Improved selective ammoxidation catalyst (1) | |
| US8835666B2 (en) | Pre calcination additives for mixed metal oxide ammoxidation catalysts | |
| CN101279252B (en) | Catalysts for the ammoxidation of alkanes | |
| US8420566B2 (en) | High efficiency ammoxidation process and mixed metal oxide catalysts | |
| EP3233272B1 (en) | Improved mixed metal oxide ammoxidation catalysts | |
| CN101428230B (en) | Catalysts for the ammoxidation of alkanes | |
| US10626082B2 (en) | Ammoxidation catalyst with selective co-product HCN production | |
| JP6526062B2 (en) | Improved selective ammoxidation catalyst | |
| JPH02111444A (en) | Ammoxidation of paraffin and catalyst thereof | |
| CN101884918B (en) | Method for preparing antimony-containing catalyst used for ammoxidation of alkane | |
| CN101992106B (en) | Alkane ammoxidation catalyst | |
| CN100333834C (en) | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof | |
| CN101992107B (en) | Method for preparing catalyst for alkane ammonia oxidation reaction | |
| CN100566822C (en) | Be used to prepare the method for alkane ammoxidation reaction catalyst | |
| CN100453171C (en) | Method for preparing catalysts for ammoxidation of alkanes | |
| CN107282094A (en) | ammonia oxidation acrylonitrile catalyst | |
| CN107282093A (en) | The catalyst of ammoxidation of propylene acrylonitrile production | |
| JP2006341179A (en) | Method for manufacturing fluidized bed of ammoxidation catalyst | |
| NO135121B (en) |
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 |