CN110937611B - System and method for improving purity of secondary salt of desulfurization waste liquid - Google Patents
System and method for improving purity of secondary salt of desulfurization waste liquid Download PDFInfo
- Publication number
- CN110937611B CN110937611B CN201911057415.1A CN201911057415A CN110937611B CN 110937611 B CN110937611 B CN 110937611B CN 201911057415 A CN201911057415 A CN 201911057415A CN 110937611 B CN110937611 B CN 110937611B
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- desulfurization waste
- salt
- liquid
- purity
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/64—Thiosulfates; Dithionites; Polythionates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/20—Thiocyanic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a method for improving the purity of secondary salt of desulfurization waste liquid. The invention takes the side salt with 50-70% of the whiteness of the desulfurization waste liquid as the raw material, adds the side salt with 50-70% into the decoloring agent, stirs to prepare supersaturated solution, and prepares the side salt with the whiteness more than or equal to 80% after solid-liquid separation and drying treatment. The beneficial effects of the invention are as follows: the desulfurization waste liquid side salt with the whiteness of 50-70% is converted into desulfurization waste liquid side salt with the whiteness of more than or equal to 80%, so that the quality requirement of industrial production can be met, the market competitiveness of the desulfurization waste liquid side salt is enhanced, and the economic benefit of the desulfurization waste liquid salt extraction device is improved.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a system and a method for improving whiteness of a solid product of a desulfurization waste liquid salt extraction device.
Background
The desulfurization waste liquid produced in the current wet desulfurization process of coking enterprises mainly adopts methods such as an evaporation concentration crystallization method, an organic solvent extraction method, a sulfuric acid oxidation liquid alkali conversion method and the like to prepare products such as thiocyanate, thiosulfate, sulfate and the like from the desulfurization waste liquid.
Because the desulfurization waste liquid contains various inorganic salts, sulfur, tar, catalyst and other pigment impurities, solid products produced by the desulfurization waste liquid salt extraction device have variegation and are easy to change color. According to the measurement method of whiteness in the general test method of GB/T13025.2-91 salt making industry, the whiteness of the desulfurization waste liquid salt extracting auxiliary salt is about 55% -70%, the quality requirement of downstream manufacturers cannot be met by the desulfurization waste liquid auxiliary salt within the whiteness range, so that the desulfurization waste liquid auxiliary salt cannot be put into factory production, the market competitiveness of the desulfurization waste liquid auxiliary salt is directly influenced, and the economic benefit of the desulfurization waste liquid salt extracting device is improved.
Disclosure of Invention
The invention aims to solve the problem that the whiteness of the secondary salt generated by the desulfurization waste liquid salt extraction device can not meet the quality requirements of manufacturers to the greatest extent, and provides a method for improving the purity of the secondary salt of the desulfurization waste liquid.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a method for improving the purity of secondary salt of desulfurization waste liquid, which is characterized by comprising the following steps:
s1, dissolving, namely continuously stirring and dissolving desulfurization waste liquid secondary salt with the whiteness of 50-70% and decolorizing agent liquid with the purity of 95-99% for 30 minutes according to the ratio of 1-4:1 at the temperature of 25 ℃ to prepare a saturated solution;
s2, solid-liquid separation, namely performing filter pressing separation on the supersaturated solution obtained in the step S1 to obtain a primary product and filtrate, and introducing the filtrate into the step S1 to be dissolved and utilized with the desulfurization waste liquid secondary salt again;
s3, drying, namely placing the primary product obtained in the S2 into a medium at the temperature of 40-60 ℃ for drying treatment to obtain a final product, and collecting the final product into a secondary salt collecting device through a pipeline.
The desulfurization waste liquid side salt in the S1 comprises any one or more of ammonium sulfate, ammonium thiosulfate, ammonium thiocyanate, sodium sulfate, sodium thiosulfate and sodium thiocyanate, and the decoloring agent liquid is a substance capable of removing useless coloring groups in certain waste water or substances and comprises any one or more of water, ethanol, methanol, chloroform and ethyl acetate.
The supersaturated solution in the step S1 is set as a mixed solution of the secondary salt of the desulfurization waste liquid and the decoloring agent liquid, and the addition amount of the secondary salt of the desulfurization waste liquid is larger than the solubility of the secondary salt of the desulfurization waste liquid in the decoloring agent liquid.
The medium for drying in S3 is set to be nitrogen.
The purity of the desulfurization waste liquid side salt is measured according to a whiteness measuring method in a general test method in the GB/T13025.2-91 salt manufacturing industry.
The invention provides a system for improving the purity of secondary salt of desulfurization waste liquid, which comprises a dissolving device, a solid-liquid separation device and a drying device which are sequentially connected through pipelines, wherein the system for improving the purity of secondary salt of desulfurization waste liquid is externally connected with a final product collecting device through a pipeline.
The dissolution device is provided as a dissolution tank for agitation, dissolution and storage of the medicament and capable of carrying a pressure load. The solid-liquid separation device is a filter press which utilizes a filter medium to dialyze liquid by applying pressure to a filter pressing object. The dryer is configured as a dryer for evaporating moisture from the material by heating to obtain a solid material of a defined moisture content, the output of the dryer being connected to the input of the final product collecting device by means of a pipe.
According to the technical scheme disclosed by the invention, the whiteness of the desulfurization waste liquid auxiliary salt is improved to more than 80% by adopting the technical means of carrying out solid-liquid separation and drying treatment on the supersaturated solution after the desulfurization waste liquid auxiliary salt with 55% -70% whiteness is mixed with the decolorizing agent liquid to prepare the supersaturated solution, so that the quality requirement of industrial production can be met, the market competitiveness of the desulfurization waste liquid auxiliary salt is enhanced, and the economic benefit of a desulfurization waste liquid salt extraction device is improved.
Drawings
The contents expressed in the drawings of the present specification and the marks in the drawings are briefly described as follows:
FIG. 1 is a schematic diagram of a system for improving the purity of secondary salts of desulfurization waste liquid according to the present invention.
FIG. 2 is a flow chart of a method for improving the purity of secondary salts of desulfurization waste liquid according to the present invention.
In the figure: 1. a dissolving device; 2. a solid-liquid separation device; 3. a drying device; 4. and a final product collection device.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
FIG. 1 is a schematic structural diagram of a system for improving the purity of secondary salts in desulfurization waste liquid according to the present invention, as shown in the following:
a system for improving the purity of the secondary salt of the desulfurization waste liquid comprises a dissolving device 1, a solid-liquid separation device 2 and a drying device 3 which are sequentially connected through pipelines, wherein the system for improving the purity of the secondary salt of the desulfurization waste liquid is externally connected with a final product collecting device 4 through the pipelines.
The dissolution device 1 is provided as a dissolution tank for agitation, dissolution and storage of the medicament and capable of carrying a pressure load. The solid-liquid separation device 2 is provided as a filter press for dialyzing a liquid by applying pressure to a press filtration object using a filter medium. The drying device 3 is arranged as a dryer for evaporating moisture from the material by heating to obtain a solid material of a defined moisture content, the output of the drying device 3 being connected by means of a pipe to the input of the end product collecting device 4.
The following examples will further illustrate the invention.
Example 1
The method for improving the purity of ammonium sulfate in the secondary salt of the desulfurization waste liquid in the embodiment comprises the following steps:
s1, dissolving, namely adding ammonium sulfate solid with the whiteness of about 50% in the secondary salt of the desulfurization waste liquid and anhydrous methanol with the purity of 95% at 25 ℃ into a dissolving device 1, stirring, wherein the mass ratio of the ammonium sulfate to the anhydrous methanol in the anhydrous methanol is 3:1, and stirring for 30min to obtain a saturated solution.
S2, solid-liquid separation, namely adding the solution exceeding saturation into the solid-liquid separation device 2 through a pipeline, performing filter pressing separation to obtain primary ammonium sulfate and filtrate, and introducing the filtrate into a dissolving device to be dissolved with ammonium sulfate with the whiteness of about 50 percent again.
S3, drying, namely drying primary ammonium sulfate obtained by filter pressing separation in a drying device 3 set to be 60 ℃ nitrogen flow to obtain ammonium sulfate solid, and collecting the ammonium sulfate into a final product collecting device through a pipeline.
The whiteness of the ammonium sulfate product obtained in the embodiment is 80% according to the whiteness measurement method in the GB/T13025.2-91 salt making industry general test method, and no obvious color change phenomenon exists after the product is placed for 1 week.
Example 2
The method for improving the purity of ammonium thiocyanate in the desulfurization waste liquid secondary salt in the embodiment comprises the following steps:
s1, dissolving, namely adding ammonium thiocyanate solid with the whiteness of about 55% and ethyl acetate with the purity of 99% at 25 ℃ in the secondary salt of the desulfurization waste liquid into a dissolving device 1, stirring to prepare a saturated solution, wherein the mass ratio of the ammonium thiocyanate to the ethyl acetate is 2:1, and stirring for 30min.
S2, solid-liquid separation, namely adding the supersaturated solution into a solid-liquid separation device 2 through a pipeline, performing filter pressing separation to obtain primary ammonium thiocyanate and filtrate, and introducing the filtrate into a dissolving device 1 to be dissolved with the ammonium thiocyanate with the whiteness of about 55 percent.
S3, drying, namely drying the separated primary ammonium thiocyanate in a drying device 3 set as a nitrogen flow at 50 ℃ to obtain an ammonium thiocyanate solid.
The whiteness of the ammonium thiocyanate product treated in the embodiment is measured to be 81% according to the whiteness measuring method in the GB/T13025.2-91 salt making industry universal test method, and no obvious color change exists after the ammonium thiocyanate product is placed for 1 month.
Example 3
The method for improving the purity of sodium sulfate in the secondary salt of the desulfurization waste liquid in the embodiment comprises the following steps:
s1, dissolving, namely adding ammonium sulfate solid with the whiteness of about 50% in the secondary salt of the desulfurization waste liquid and absolute ethyl alcohol with the purity of 97% at 25 ℃ into a dissolving device 1, stirring, wherein the mass ratio of sodium sulfate to ethyl alcohol is 4:1, and continuously stirring for 30min to obtain the supersaturated solution.
S2, solid-liquid separation, namely adding the solution exceeding saturation into a solid-liquid separation device 2 through a pipeline, performing filter pressing separation to obtain primary sodium sulfate and filtrate, and introducing the filtrate into a dissolution device 1 to be dissolved with sodium sulfate with the whiteness of about 50 percent again.
S3, drying, namely drying primary ammonium sulfate obtained by filter pressing separation in a drying device 3 set as a nitrogen flow at 40 ℃ to obtain sodium sulfate solid, and collecting the ammonium sulfate into a final product collecting device through a pipeline.
The whiteness of the ammonium sulfate product obtained in the embodiment is 80% according to the whiteness measurement method in the GB/T13025.2-91 salt making industry general test method, and no obvious color change phenomenon exists after the product is placed for 1 month.
Example 4
The method for improving the purity of sodium thiosulfate in the desulfurization waste liquid secondary salt in the embodiment comprises the following steps:
s1, dissolving, namely adding sodium thiosulfate solid with the whiteness of about 70% in the secondary salt of the desulfurization waste liquid into absolute ethyl alcohol with the purity of 97% at 25 ℃ to prepare a saturated solution, wherein the mass ratio of the sodium thiosulfate to the absolute ethyl alcohol is 1:1, and continuously stirring for 30min.
S2, solid-liquid separation, namely adding the supersaturated solution into a solid-liquid separation device through a pipeline, and performing filter pressing separation to obtain primary sodium thiosulfate and filtrate, and introducing the filtrate into a dissolving device to be dissolved with sodium thiosulfate with the whiteness of about 70 percent again.
S3, drying, namely drying the separated primary sodium thiosulfate in a drying device 3 set as a nitrogen flow at 40 ℃ to obtain a sodium thiosulfate product.
The whiteness of the sodium thiosulfate product treated in the embodiment is measured to be 82% according to the whiteness measuring method in the general test method of GB/T13025.2-91 salt making industry, and no obvious color change exists after the sodium thiosulfate product is placed for 1 week.
According to the technical scheme disclosed by the invention, the whiteness of the desulfurization waste liquid auxiliary salt is improved to more than 80% by adopting the technical means of carrying out solid-liquid separation and drying treatment on the supersaturated solution after the desulfurization waste liquid auxiliary salt with 55% -70% whiteness is mixed with the decolorizing agent liquid to prepare the supersaturated solution, so that the quality requirement of industrial production can be met, the market competitiveness of the desulfurization waste liquid auxiliary salt is enhanced, and the economic benefit of a desulfurization waste liquid salt extraction device is improved.
While the invention has been described above with reference to the accompanying drawings, it will be apparent that the invention is not limited to the above embodiments, but is capable of being modified or applied directly to other applications without modification, as long as various insubstantial modifications of the method concept and technical solution of the invention are adopted, all within the scope of the invention.
Claims (1)
1. A method for improving the purity of secondary salt of desulfurization waste liquid, which is characterized in that the system for improving the purity of the secondary salt of the desulfurization waste liquid comprises a dissolving device, a solid-liquid separation device and a drying device which are sequentially connected through a pipeline, wherein the system for improving the purity of the secondary salt of the desulfurization waste liquid is externally connected with a final product collecting device through the pipeline, and the dissolving device is arranged as a dissolving tank which is used for stirring, dissolving and storing medicaments and can bear pressure load; the solid-liquid separation device is a filter press which utilizes a filter medium and applies pressure to a filter pressing object to dialyze liquid, the drying device is a dryer which is used for vaporizing moisture in materials and escaping through heating so as to obtain solid materials with specified moisture content, and the output end of the dryer is connected to the input end of the final product collecting device through a pipeline; a method for purifying the secondary salt purity of a desulfurization waste liquid using a system for increasing the secondary salt purity of the desulfurization waste liquid, comprising the steps of:
s1, dissolving, namely continuously stirring and dissolving desulfurization waste liquid side salt with the whiteness of 50-70% and decolorizing agent liquid with the purity of 95-99% for 30 minutes according to the proportion of (1-4) to 1 at the temperature of 25 ℃ to obtain a supersaturated solution, wherein the desulfurization waste liquid side salt comprises any one or more of ammonium sulfate, ammonium thiosulfate, ammonium thiocyanate, sodium sulfate, sodium thiosulfate and sodium thiocyanate, and the decolorizing agent liquid is a substance capable of removing useless dyeing groups in certain waste water or substances, and comprises any one or more of ethanol, methanol, chloroform and ethyl acetate; the supersaturated solution is set as a mixed solution of desulfurization waste liquid auxiliary salt and decolorant liquid, and the addition amount of the desulfurization waste liquid auxiliary salt is larger than the solubility of the desulfurization waste liquid auxiliary salt in the decolorant liquid;
s2, solid-liquid separation, namely performing filter pressing separation on the supersaturated solution obtained in the step S1 to obtain a primary product and filtrate, and introducing the filtrate into the step S1 to be dissolved and utilized with the desulfurization waste liquid secondary salt again;
s3, drying, namely placing the primary product obtained in the S2 into a medium at the temperature of 40-60 ℃ for drying treatment to obtain a final product, and collecting the final product into a secondary salt collecting device through a pipeline, wherein the medium for drying is set to be nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911057415.1A CN110937611B (en) | 2019-11-01 | 2019-11-01 | System and method for improving purity of secondary salt of desulfurization waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911057415.1A CN110937611B (en) | 2019-11-01 | 2019-11-01 | System and method for improving purity of secondary salt of desulfurization waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110937611A CN110937611A (en) | 2020-03-31 |
| CN110937611B true CN110937611B (en) | 2023-05-23 |
Family
ID=69906466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911057415.1A Active CN110937611B (en) | 2019-11-01 | 2019-11-01 | System and method for improving purity of secondary salt of desulfurization waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110937611B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001690A (en) * | 2010-11-24 | 2011-04-06 | 陈君华 | Method for preparing industrial anhydrous sodium sulfate |
| CN102259894A (en) * | 2011-05-27 | 2011-11-30 | 山东美科动力有限公司 | Comprehensive recovery process of secondary salts from coking plant desulfurization waste liquid |
| CN102614767A (en) * | 2011-01-28 | 2012-08-01 | 苏云学 | Apparatus for improving ammonium sulfate purity by ammonia desulfurization |
| CN102874845A (en) * | 2012-10-15 | 2013-01-16 | 安徽工业大学 | Extraction of ammonium thiocyanate from coking and desulfurization waste liquid |
| CN103342373A (en) * | 2013-06-08 | 2013-10-09 | 太原理工大学 | Decoloring method for ammonium thiocyanate salt extracted from coking desulfurization waste liquid |
| CN103663497A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving whiteness of sodium thiocyanate in coking desulfurization waste liquid |
| WO2016029614A1 (en) * | 2014-08-25 | 2016-03-03 | 湖南江冶机电科技股份有限公司 | Method and apparatus for recovering anhydrous sodium sulfate from filtrate after purification treatment of desulfurated lead plasters |
| CN110054203A (en) * | 2019-04-12 | 2019-07-26 | 河海大学 | A kind of method of resource of industrial waste salt |
-
2019
- 2019-11-01 CN CN201911057415.1A patent/CN110937611B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001690A (en) * | 2010-11-24 | 2011-04-06 | 陈君华 | Method for preparing industrial anhydrous sodium sulfate |
| CN102614767A (en) * | 2011-01-28 | 2012-08-01 | 苏云学 | Apparatus for improving ammonium sulfate purity by ammonia desulfurization |
| CN102259894A (en) * | 2011-05-27 | 2011-11-30 | 山东美科动力有限公司 | Comprehensive recovery process of secondary salts from coking plant desulfurization waste liquid |
| CN102874845A (en) * | 2012-10-15 | 2013-01-16 | 安徽工业大学 | Extraction of ammonium thiocyanate from coking and desulfurization waste liquid |
| CN103342373A (en) * | 2013-06-08 | 2013-10-09 | 太原理工大学 | Decoloring method for ammonium thiocyanate salt extracted from coking desulfurization waste liquid |
| CN103663497A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving whiteness of sodium thiocyanate in coking desulfurization waste liquid |
| WO2016029614A1 (en) * | 2014-08-25 | 2016-03-03 | 湖南江冶机电科技股份有限公司 | Method and apparatus for recovering anhydrous sodium sulfate from filtrate after purification treatment of desulfurated lead plasters |
| CN110054203A (en) * | 2019-04-12 | 2019-07-26 | 河海大学 | A kind of method of resource of industrial waste salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110937611A (en) | 2020-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102239185A (en) | A process for recycling cellulose acetate ester waste | |
| CN101434970A (en) | Double decomposition precipitation transformation production method of potassium citrate | |
| CN102010318B (en) | Production method of mixed long carbon chain dibasic acid | |
| CN104098215B (en) | The treatment process of acid waste water in 2-ethyl-anthraquinone production process | |
| CN103663497A (en) | Method for improving whiteness of sodium thiocyanate in coking desulfurization waste liquid | |
| CN110937611B (en) | System and method for improving purity of secondary salt of desulfurization waste liquid | |
| CN111804704B (en) | Method for treating tetrachloro sodium aluminate solid slag | |
| CN102746354A (en) | Method for extracting tylosin by tylosin fermentation broth | |
| CN101555238B (en) | Method for tetrahydrofuran recycling | |
| CN106277045B (en) | The technique that a kind of titanium dioxide hydrochloric acid residue resource recycles | |
| CN109052477A (en) | A kind of sodium tungstate preparation process being used to prepare ammonium paratungstate | |
| DE102006059760B4 (en) | Process for the continuous production of highly pure urea solution | |
| CN218665427U (en) | Equipment system for preparing ammonium dihydrogen phosphate by recycling waste phosphoric acid | |
| CN111362280A (en) | System and method for preparing sodium thiocyanate and sodium sulfate from desulfurization waste liquid | |
| CN112321418A (en) | Refining method of long-chain dibasic acid | |
| CN215403103U (en) | Impurity removing device for phosphoric acid in preparation of activated carbon by phosphoric acid method | |
| CN100469750C (en) | Method of extracting calcium gluconate from mother liquid after calcium gluconate crystallization | |
| DE2525370C3 (en) | Process for working up proteins produced by fermentation in fermenters, which are then subjected to drying | |
| CN107721887A (en) | A kind of preparation method of highly acid blue dyes | |
| CN110877913B (en) | Ammonium sulfate purification method for ammonia desulfurization waste liquid production | |
| CN104944446B (en) | A kind of method extracting potassium nitrate reagent in dyeing waste water | |
| CN106866441A (en) | A kind of preparation method of high-purity grade of Ferric Sodium Edetate | |
| AT413985B (en) | METHOD AND DEVICE FOR CONVERSION AND UTILIZATION OF BY-PRODUCTS OF THE MILK-PROCESSING INDUSTRY | |
| CN103922407A (en) | Method for recycling phosphorus molybdenum heteropolyacid | |
| CN112239413A (en) | Purification and closed production method of glycine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |