CN106430223B - A method of preparing high-specific surface area white carbon using fluosilicate - Google Patents
A method of preparing high-specific surface area white carbon using fluosilicate Download PDFInfo
- Publication number
- CN106430223B CN106430223B CN201610903230.8A CN201610903230A CN106430223B CN 106430223 B CN106430223 B CN 106430223B CN 201610903230 A CN201610903230 A CN 201610903230A CN 106430223 B CN106430223 B CN 106430223B
- Authority
- CN
- China
- Prior art keywords
- fluosilicate
- white carbon
- surface area
- specific surface
- aqueous solution
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of methods preparing high-specific surface area white carbon using fluosilicate.This method includes：It is first added into aqueous solution and contains alcoholic extract hydroxyl group, then fluosilicate is added in aqueous solution, after stirring evenly, ammonium hydroxide is added dropwise, the reaction was continued；It is aged after the completion of reaction, be filtered, washed, dry, obtain high-specific surface area white carbon.Operating procedure of the present invention is simple, and yield is up to 98% or more, and low energy consumption, and prepared white carbon BET specific surface area reaches HG/T 3061-2009 A class standards, can be used for multiple industries such as rubber, agriculture chemistry, papermaking, and application prospect is extensive.
Description
Technical field
The present invention relates to a kind of methods preparing high-specific surface area white carbon using fluosilicate, belong to white carbon and prepare skill
Art field.
Background technology
Fluosilicate is the by-product being fluorinated in work and phosphorous chemical industry, can be used as product and directly applies to building materials industry.
But the added value of product is low, purposes is narrow, and economic benefit is poor, thus unsalable situation usually occurs, has seriously affected manufacturer
The enthusiasm for recycling fluosilicate, causes the waste of fluorine, silicon resource, polluted environment, more largely restrict phosphorus
The sound development of chemical industry.Therefore, the downstream product of fluorine, especially added value height and the big product of market capacity, maximum limit are developed
Degree ground digestion fluosilicate, recycling fluorine, reduce environmental pollution at silicon resource, improve the market value of fluosilicate, have compeled in eyebrow
Eyelash.
White carbon, chemical composition are hydrated SiO 2, are a kind of environmental protection, the auxiliary agent that has excellent performance, are widely used in rubber
The multiple fields such as glue, agriculture chemistry, papermaking are important chemical products, have many advantages, such as dosage is big, added value is high.Fluorine
The main component of silicate is three kinds of fluorine, silicon, hydrogen elements, can prepare white carbon by special process extraction as silicon source.Cause
This, fully develops and uses fluosilicate, using its as raw material prepare high quality white carbon, be improve its application value and
Economic benefit, the effective means to reduce environmental pollution.
The method that Chinese patent literature CN1337355A discloses sodium fluorosilicate ammoniating preparing high strengthening white carbon, the invention carry
Na is gone out2SiF6Substep ammoniated treatment technique, first once by the Na of total amount 25-50%2SiF6With 5-20% ammonium hydroxide at 30-45 DEG C
Lower reaction is conducive to the generation of small glue core, remaining Na then is added again or by several times2SiF6With ammonium hydroxide at 50-70 DEG C
After ageing, through being filtered, washed, drying, white carbon is made in reaction.The invention product can be used as shoemaking, tire supporting material.
But it is low (5~10%) with sodium fluoride solution concentration prepared by the inventive method, single batch low output consumes energy in production process
Height, and increase the processing cost of follow-up sewage.Chinese patent document CN104030297A discloses a kind of novel utilization fluorine
Silicic acid produces the production technology of sodium fluoride co-producing white carbon black, and with fluosilicic acid, waterglass (sodium metasilicate), soda ash is main material production
High-purity silicon dioxide and coproduction sodium fluoride technique, and the waste water fluorination mother liquid of sodium recycling that sodium fluoride will be produced.But it should
It invents the soda ash used and generates great amount of carbon dioxide in prodan reaction process, greenhouse effects can be aggravated, be unfavorable for ecology
Environment sustainable development.
Chinese patent application file CN101376500A is related to a kind of method preparing white carbon, with fluosilicic acid, waterglass
For primary raw material, following steps are specifically included：(1) waterglass of a concentration of 18%-25% is added in seed mixer, water is added to make life
At white carbon solid content reach 1-3%；(2) fluosilicic acid is rapidly joined under room temperature, stirs 30min, endpoint pH 6.5-
8.5；(3) crystal seed is warming up to 70-90 DEG C, fluosilicic acid is added in crystal seed and is stirred evenly, adding water keeps the white carbon of generation solid
Content reaches 2-5%, and waterglass is added in the mixed liquor of crystal seed and fluosilicic acid constant temperature at a temperature of 80~90 DEG C in 30min,
Continue to stir 30min after adding material, ensures that the reaction was complete with waterglass for fluosilicic acid, keep the temperature 50-60min, endpoint pH 7-8；(4)
The solution of good heat insulation in step (3) is filtered, filter cake is after level water washing, drying white carbon finished product.The invention
Method cost it is relatively low and raw material is easy to get, but have by-product sodium fluosilicate generation in reaction process, can have to the yield of white carbon
It influences.Chinese patent document CN103420383A disclosure of the invention one kind preparing vapor phase method hard charcoal with phosphatic fertilizer by-product fluosilicate
Black and anhydrous hydrofluoric acid method, phosphate fertilizer by-product fluosilicate pyrogenically prepared ocratation at 200~400 DEG C, by filtering
After device removes dust, is washed by 93~98% concentrated sulfuric acids and remove moisture and impurity, in hydrolysis reactor, ocratation and sky
Gas, hydrogen by volume 1：2：After 0.05~0.3 ratio mixing, occur high-temperature hydrolysis, it is aggregated, separation, dedusting, cold
Solidifying, rectifying respectively obtains fume colloidal silica and anhydrous hydrofluoric acid.But in the preparation process, pyroreaction, energy consumption is employed many times
It is high.
In conclusion the preparation of white carbon is high in the presence of energy consumption in the prior art, environment is unfriendly, of high cost, yield is low, work
Skill process is complicated, is unsuitable for the problems such as large-scale production, seriously affects economic benefit and social benefit.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of high-specific surface area white carbon is prepared using fluosilicate
Method, have the advantages that low energy consumption, period are short, purity is high, simple process, of low cost, high income and with specific surface area it is high.
Technical solution of the present invention is as follows：
A method of high-specific surface area white carbon being prepared using fluosilicate, is included the following steps：
(1) additive containing alcoholic extract hydroxyl group is added to the water, 40~90 DEG C of 5~20min of stirring obtain aqueous solution；It is described containing
The additive of alcoholic extract hydroxyl group and the mass ratio of water are 0.001~0.1: 1；
(2) fluosilicate is added in step (1) in aqueous solution obtained, 40~90 DEG C of 10~40min of stirring obtain fluorine
Silicate solutions；The mass ratio of the fluosilicate and step (1) described aqueous solution is 10~40: 100；
(3) at 40~90 DEG C, ammonium hydroxide is added dropwise in the silicate fluoride solution prepared to step (2) while stirring, drips
It is 2~30min between added-time, continues to stir after being added dropwise to complete, reacts 10~60min；The molar ratio of the ammonium hydroxide and fluosilicate
It is 1.1~1.7: 1；
(4) solution after reacting step (3) is aged 10~60min at 40~90 DEG C, filters while hot, with 40~90 DEG C
The deionized water of temperature is washed, dried at 105~110 DEG C to get.
The white carbon high-specific surface area that the method for the present invention is prepared using fluosilicate is in 170 ㎡/g~220 ㎡/g.
, according to the invention it is preferred to, the additive containing alcoholic extract hydroxyl group described in step (1) is selected from methanol, ethyl alcohol, the third three
The mass ratio of the mixture of one or more of alcohol or n-butanol, the additive and water is 0.002~0.03: 1.
, according to the invention it is preferred to, the mass ratio of fluosilicate and the aqueous solution of step (1) described in step (2) is
15~25: 100；Further preferably, the fluosilicate is potassium fluosilicate or prodan.
, according to the invention it is preferred to, the molar ratio of ammonium hydroxide and fluosilicate described in step (3) is 1.2~1.5: 1.
, according to the invention it is preferred to, the time for adding of the ammonium hydroxide described in step (3) is 3~15min；Further preferably
Ammonium hydroxide time for adding be 5~10min.
, according to the invention it is preferred to, step (1), (2), the whipping temp described in (3) they are 50~70 DEG C.
, according to the invention it is preferred to, the Aging Temperature described in step (4) is 50~70 DEG C.
, according to the invention it is preferred to, the temperature of the deionized water described in step (4) is 50~70 DEG C.
It is not specified according to the prior art in the above preparation method of the present invention.
The technical characterstic and excellent results of the present invention：
1, the present invention prepares high-specific surface area white carbon using fluosilicate, before aqueous solution is added in fluosilicate, carries
Preceding additive of the addition containing alcoholic extract hydroxyl group changes aqueous environment, prevents the reunion between the silica of generation；Pass through regulation and control
The rate of addition of ammonium hydroxide reduces the agglomerating force of silica to control the nucleation rate of silica；Hard charcoal is washed using warm water
It is black, prevent the silica particles caused by temperature decrease from assembling, the specific surface area of product is high, white carbon prepared by the method for the present invention
Specific surface area is up to 220 ㎡/g.
2, the method for the present invention is with short production cycle, and single batch white carbon can prepare completion in most fast half an hour.The present invention
Reaction temperature is mild in preparation process, avoids pyroreaction, reduces energy consumption.
3, raw material of the present invention is cheap is easy to get, and operating procedure is easy, and product purity is high, and the white carbon purity of preparation is with fluorine content
Indicate to be only 0.05%~0.25%.
4, the yield of white carbon obtained by the method for the present invention is high, up to 98% or more.
5, the method for the present invention is suitable for the industrialized production of extensive high yield, can produce 1-5 tons of white carbon per year.
In conclusion the method for the present invention have low energy consumption, the period is short, purity is high, high-specific surface area, simple process, cost
The advantage cheap, yield is high, yield is big etc..
Description of the drawings
Fig. 1 is the nitrogen adsorption desorption curve graph of white carbon prepared by embodiment 1, wherein abscissa is adsorbance, unit：
ml/g；Ordinate is relative pressure, unit：p/po。
Specific implementation mode
With reference to embodiment, the present invention is described further, but not limited to this.
Embodiment 1：
A method of high-specific surface area white carbon being prepared using fluosilicate, steps are as follows：
(1) it weighs 0.8g ethyl alcohol to be added in 100g water, 55 DEG C of stirring 5min；
(2) 20g potassium fluosilicates are added to aqueous solution obtained in step (1), 55 DEG C of stirring 30min；
(3) dropwise addition ammonium hydroxide 32g, 5min in 60 DEG C of stirrings is warming up to be added dropwise, continue to be stirred to react after being added dropwise to complete
30min；
It is aged 30min at (4) 60 DEG C, is filtered while hot, filter cake filtrates are washed to neutrality using 55 DEG C of deionized waters, 105 DEG C
It is dry, white carbon 5.35g, 215.5 ㎡ of specific surface area/g are obtained, reach HG/T 3061-2009 A class standards, yield is
98.1%, fluorine content 0.11%.
Embodiment 2：
A method of high-specific surface area white carbon being prepared using fluosilicate, steps are as follows：
(1) it weighs 0.3g n-butanols to be added in 100g water, 70 DEG C of stirring 5min；
(2) 25g prodans are added to aqueous solution obtained in step (1), 70 DEG C of stirring 20min；
Dropwise addition ammonium hydroxide 45g, 10min are added dropwise, continue to be stirred to react 20min after being added dropwise to complete in (3) 75 DEG C of stirrings；
It is aged 15min at (4) 70 DEG C, is filtered while hot, filter cake filtrates are washed to neutrality using 60 DEG C of deionized waters, 105 DEG C
It is dry, white carbon 7.87g, 186.4 ㎡ of specific surface area/g are obtained, reach HG/T 3061-2009 B class standards, yield is
98.5%, fluorine content 0.08%.
Embodiment 3：
A method of high-specific surface area white carbon being prepared using fluosilicate, steps are as follows：
(1) 0.5kg ethyl alcohol and 0.1kg n-butanols, 60 DEG C of stirring 10min are sequentially added in 80kg water；
(2) 15kg potassium fluosilicates are added in step (1) in aqueous solution obtained, 60 DEG C of stirring 25min；
Dropwise addition ammonium hydroxide 25kg, 5min are added dropwise, continue to be stirred to react 30min after being added dropwise to complete in (3) 60 DEG C of stirrings；
It is aged 25min at (4) 60 DEG C, is filtered while hot, filter cake filtrates are washed to neutrality using 60 DEG C of deionized waters, 105 DEG C
It is dry, white carbon 4.01kg, 197.3 ㎡ of specific surface area/g are obtained, reach HG/T 3061-2009 A class standards, yield is
98.0%, fluorine content 0.11%.
Embodiment 4：
A method of high-specific surface area white carbon being prepared using fluosilicate, steps are as follows：
(1) 0.4kg methanol and 0.2kg glycerine, 50 DEG C of stirring 10min are sequentially added in 90kg water；
(2) 20kg prodans are added in step (1) in aqueous solution obtained, 50 DEG C of stirring 30min；
(3) dropwise addition ammonium hydroxide 40kg, 10min in 55 DEG C of stirrings is warming up to be added dropwise, continue to be stirred to react after being added dropwise to complete
40min；
It is aged 30min at (4) 55 DEG C, is filtered while hot, filter cake filtrates are washed to neutrality using 55 DEG C of deionized waters, 105 DEG C
It is dry, white carbon 6.30kg, 173.7 ㎡ of specific surface area/g are obtained, reach HG/T 3061-2009 B class standards, yield is
98.6%, fluorine content 0.06%.
Experimental example：
Based on the preparation method of embodiment 1, ammonium hydroxide time for adding pair is investigated by changing the experiment of ammonium hydroxide time for adding
It is as a result as follows in the influence of the specific surface area of product white carbon, purity and yield：
1 ammonium hydroxide time for adding contrast and experiment of table
Claims (8)
1. a kind of method preparing high-specific surface area white carbon using fluosilicate, which is characterized in that include the following steps：
(1) take a certain amount of additive containing alcoholic extract hydroxyl group in water, 40~90 DEG C of 5~20min of stirring obtain aqueous solution；It is described to contain
The mass ratio of the additive and water that have alcoholic extract hydroxyl group is 0.001~0.1: 1；The additive containing alcoholic extract hydroxyl group be selected from methanol,
The mixture of one or more of glycerine or n-butanol；
(2) fluosilicate is added in step (1) in aqueous solution obtained, 40~90 DEG C of 10~40min of stirring obtain fluosilicic acid
Salting liquid；The mass ratio for the aqueous solution that the fluosilicate is prepared with step (1) is 10~40: 100；The fluosilicate is
Potassium fluosilicate or prodan；
(3) at 40~90 DEG C, ammonium hydroxide is added dropwise in the silicate fluoride solution prepared to step (2) while stirring, when dropwise addition
Between be 3~15min, continue to stir after being added dropwise to complete, react 10~60min；The molar ratio of the ammonium hydroxide and fluosilicate is 1.1
~1.7: 1；
(4) solution after reacting step (3) is aged 10~60min at 40~90 DEG C, filters while hot, with 40~90 DEG C of temperature
Deionized water washing, dry at 105~110 DEG C to get.
2. the method as described in claim 1, which is characterized in that in step (1), the additive containing alcoholic extract hydroxyl group and water
Mass ratio is 0.002~0.03: 1.
3. the method as described in claim 1, which is characterized in that the fluosilicate described in step (2) was prepared with step (1)
The mass ratio of aqueous solution is 15~25: 100.
4. the method as described in claim 1, which is characterized in that the molar ratio of ammonium hydroxide and fluosilicate described in step (3)
It is 1.2~1.5: 1.
5. the method as described in claim 1, which is characterized in that the time for adding of the ammonium hydroxide described in step (3) be 5~
10min。
6. the method as described in claim 1, which is characterized in that step (1), (2), the whipping temp described in (3) be 50~
70℃。
7. the method as described in claim 1, which is characterized in that the Aging Temperature described in step (4) is 50~70 DEG C.
8. the method as described in claim 1, which is characterized in that the temperature of the deionized water described in step (4) is 50~70
℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610903230.8A CN106430223B (en) | 2016-10-17 | 2016-10-17 | A method of preparing high-specific surface area white carbon using fluosilicate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610903230.8A CN106430223B (en) | 2016-10-17 | 2016-10-17 | A method of preparing high-specific surface area white carbon using fluosilicate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106430223A CN106430223A (en) | 2017-02-22 |
| CN106430223B true CN106430223B (en) | 2018-11-02 |
Family
ID=58175215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610903230.8A Active CN106430223B (en) | 2016-10-17 | 2016-10-17 | A method of preparing high-specific surface area white carbon using fluosilicate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106430223B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1337355A (en) * | 2001-09-25 | 2002-02-27 | 天津化工研究设计院 | Sodium fluorosilicate ammoniating process of producing high reinforcing silica white |
| CN101139094A (en) * | 2007-08-24 | 2008-03-12 | 云南云天化国际化工股份有限公司 | Method for preparing big-compensating forcing white carbon black and high concentration ammonium fluoride through aminating of fluosilicic acid |
| CN103112873A (en) * | 2013-02-26 | 2013-05-22 | 山东金正大生态工程股份有限公司 | Method for preparing high-purity potassium fluoride and co-producing white carbon black by adopting potassium fluosilicate |
| CN103121699A (en) * | 2013-02-26 | 2013-05-29 | 贵州金正大生态工程有限公司 | Method for preparing potassium fluoride by utilizing potassium fluosilicate |
| RU2492142C1 (en) * | 2012-04-28 | 2013-09-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Method of producing sodium silicofluoride |
-
2016
- 2016-10-17 CN CN201610903230.8A patent/CN106430223B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1337355A (en) * | 2001-09-25 | 2002-02-27 | 天津化工研究设计院 | Sodium fluorosilicate ammoniating process of producing high reinforcing silica white |
| CN101139094A (en) * | 2007-08-24 | 2008-03-12 | 云南云天化国际化工股份有限公司 | Method for preparing big-compensating forcing white carbon black and high concentration ammonium fluoride through aminating of fluosilicic acid |
| RU2492142C1 (en) * | 2012-04-28 | 2013-09-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Method of producing sodium silicofluoride |
| CN103112873A (en) * | 2013-02-26 | 2013-05-22 | 山东金正大生态工程股份有限公司 | Method for preparing high-purity potassium fluoride and co-producing white carbon black by adopting potassium fluosilicate |
| CN103121699A (en) * | 2013-02-26 | 2013-05-29 | 贵州金正大生态工程有限公司 | Method for preparing potassium fluoride by utilizing potassium fluosilicate |
Non-Patent Citations (3)
| Title |
|---|
| 乙醇添加量对白炭黑性质的影响;刘晓等;《无机盐工业》;20130731;第45卷(第7期);24-27 * |
| 氨水和氟硅酸钠制备氟化钠和白炭黑的实验研究;叶红勇等;《广州化工》;20160331;第44卷(第5期);87-88、96 * |
| 氨解沉淀法白炭黑的研究进展;周俊生等;《无机盐工业》;20120331;第44卷(第3期);5-7 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106430223A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104326475B (en) | A kind of method utilizing silicofluoric acid to prepare Potassium monofluoride co-producing white carbon black | |
| CN102674367B (en) | Method for preparing ammonium fluorosilicate by utilizing fluorine-containing white slime in anhydrous hydrogen fluoride production | |
| CN103601217B (en) | Sodium fluoride production process and sodium fluoride mother liquor recycling process | |
| CN101214960B (en) | Integrated utilization method for phosphorus chemical industry byproduct fluorosilicic acid | |
| CN103466637A (en) | Method for producing precipitate silicon dioxide by using sodium bicarbonate to control supersaturation degree | |
| CN103043684A (en) | Method for producing ammonium hydrogen fluoride by recovering fluorine in wet process phosphoric acid tail gas | |
| CN105036141A (en) | Method for producing nanosilicon dioxide and by-product hydrochloric acid through chlorosilane waste gas | |
| CN103121699B (en) | A kind of method that potassium fluosilicate prepares potassium fluoride | |
| CN110562991A (en) | Production method of white carbon black for high-oil-absorption carrier | |
| CN106430223B (en) | A method of preparing high-specific surface area white carbon using fluosilicate | |
| CN105271244B (en) | Method for synthesis of mesoporous molecular sieve and byproduct cryolite by use of fluosilicic acid | |
| CN102874821A (en) | Preparation method of high-purity silicon dioxide | |
| CN101734667B (en) | Process for producing precipitated white carbon black by silicon tetrachloride | |
| CN104445219A (en) | Preparation method of white carbon black | |
| CN102976356B (en) | Method for preparing high-quality ammonium hydrogen fluoride from fluorine and silicon compound | |
| CN102491342B (en) | Method for preparing white carbon black by using fluosilicic acid gas ammonification process | |
| CN105752994A (en) | Method for preparing white carbon black from graphite tailings | |
| CN111732104A (en) | Method for preparing potassium fluosilicate from fluorine-containing wastewater | |
| CN106006557B (en) | A kind of method of chlorosilane raffinate production hydrogen chloride gas | |
| CN109179429A (en) | A kind of method that chlorosilane raffinate prepares meso-porous nano silica | |
| CN103539130A (en) | Technological method for preparing white carbon black from potassium feldspar | |
| CN101676213A (en) | Method for dry preparation of barium fluorosilicate and barium fluoride | |
| CN204981169U (en) | Utilize device of chlorosilane waste gas production nanometer silica and by -product hydrochloric acid | |
| CN106673015B (en) | The method for producing high-purity ammonium fluoride using sodium bifluoride waste residue | |
| CN101462724A (en) | Method for preparing nano silicon dioxide from wet process phosphoric acid by-product sodium fluosilicate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |