CN102262086B - Method for precisely measuring uranium by extraction photometry - Google Patents
Method for precisely measuring uranium by extraction photometry Download PDFInfo
- Publication number
- CN102262086B CN102262086B CN 201110097471 CN201110097471A CN102262086B CN 102262086 B CN102262086 B CN 102262086B CN 201110097471 CN201110097471 CN 201110097471 CN 201110097471 A CN201110097471 A CN 201110097471A CN 102262086 B CN102262086 B CN 102262086B
- Authority
- CN
- China
- Prior art keywords
- uranium
- extraction
- chromium
- potassium dichromate
- 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
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 44
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000000605 extraction Methods 0.000 title claims abstract description 35
- 238000005375 photometry Methods 0.000 title abstract description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000005259 measurement Methods 0.000 claims abstract description 25
- 238000002798 spectrophotometry method Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 10
- HNVACBPOIKOMQP-UHFFFAOYSA-N uranium(4+) Chemical compound [U+4] HNVACBPOIKOMQP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical group CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000005185 salting out Methods 0.000 claims description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000005070 sampling Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003758 nuclear fuel Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 241000030614 Urania Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- AAORDHMTTHGXCV-UHFFFAOYSA-N uranium(6+) Chemical compound [U+6] AAORDHMTTHGXCV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for precisely measuring uranium by an extraction spectrophotometry, which comprises the steps of weighing a uranium sample, pretreating, adjusting the valence to uranium (IV), adding excessive potassium dichromate after the valence is adjusted to uranium (IV) to oxidize the uranium (IV) to uranium (VI), then adding an organic solvent to extract excessive chromium (VI), and measuring chromium in an organic phase by a spectrophotometry, wherein the excessive potassium dichromate is added so that the added excessive amount accounts for 0.3-0.5% of the total amount of potassium dichromate. The method for precisely measuring uranium by the extraction photometry provided by the invention has the advantages of high precision, high selectivity, simplicity in operation, small sampling amount, accurate and reliable measurement result and easiness in realization.
Description
Technical field
The present invention relates to the nuclear fuel cycle technical field, particularly a kind of method of extraction spectrophotometric method micrometric measurement uranium.
Background technology
Uranium is important nuclear fuel, and the micrometric measurement technology of uranium is having critical role aspect the links of nuclear fuel cycle and the nuclear safeguards.
Have bibliographical information to adopt direct photometry micrometric measurement uranium content, the method uranium sampling amount is 2.5g, and the measurement result relative standard deviation is 0.05%.The method is directly carried out the mensuration of chromium (VI) without separation.Source of error is many, and the uncertainty component of introducing is many; Mo (VI), Cu (II), Fe (III), V (V) and U (VI) etc. measure the chromium (VI) of surplus all interference, in order to eliminate the interference of foreign ion, must increase the uranium sampling amount, with the accuracy of raising method.The method adds excessively with the titrant potassium dichromate is disposable, the vessel aridity is had relatively high expectations, and poor stability, uranium sampling amount is large.And potentiometric titration and other spectrophotometric method micrometric measurement uranium need to add the reagent vanadium sulfate acyl in the mensuration process, and this reagent needs voluntarily preparation before mensuration, and this is the main cause that causes the procedure complexity.
The applicant did concise and to the point report to the method for extraction spectrophotometric method micrometric measurement uranium content in 2008 in China Atomic Energy Science Research Institute's annual report, but the thinking that the applicant sets up the method just briefly set forth in article, and the accuracy of the method is set forth and verified.Concrete technology step and the parameter of the unexposed method of article, and concrete technology step and parameter are to realize the gordian technique of pin-point accuracy and high precision.
Summary of the invention
The present invention has overcome deficiency of the prior art, provide a kind of high precision, simple to operate, sampling amount is little, measurement result is accurate, the method for extraction spectrophotometric method micrometric measurement uranium reliable, that easily realize.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of method of extraction spectrophotometric method micrometric measurement uranium, comprise and take by weighing uranium sample, pre-service, readjust prices to uranium (IV), add excessive potassium dichromate to the uranium (IV) with U (IV) oxidation U (VI) described the price modification, then the chromium (VI) that adds the organic solvent extraction surplus, adopt the chromium in the spectrophotometry organic phase, key is that the excessive potassium dichromate of described adding accounts for 0.3%～0.5% of potassium dichromate total amount for adding excess quantity.
Add salting-out agents sodium chloride in the process of described extraction of chromium.Add excessive potassium dichromate to the uranium (IV) and do not add vanadium sulfate acyl solution in U (IV) oxidation U (VI) process described the price modification.The ratio of the organic phase after the described extraction of chromium and water is 1: 2～1: 3, and the ratio of preferably selecting organic phase and water is 1: 3.Described pre-service is for adding the uranium sample that takes by weighing successively strong phosphoric acid, potassium bichromate solution, sulfuric acid solution, the stirring of sulfaminic acid solution.Described adding organic solvent extraction chromium (VI) is for adding successively behind surfactant Tritonx-100 solution, DPC solution, the organic solvent fully oscillation extraction.Described organic solvent is isoamylol.
Compared with prior art, the invention has the beneficial effects as follows:
The potassium dichromate excess quantity that adds in this method accounts for 0.3%～0.5% of potassium dichromate total amount, can greatly improve like this accuracy and the precision of measurement result.Add excessive potassium dichromate to the uranium (IV) and do not add vanadium sulfate acyl solution in U (IV) oxidation U (VI) process readjusting prices, avoided the interference of vanadium to measuring, saved simultaneously the time for preparing voluntarily vanadium sulfate acyl.Excessive chromium (VI) is measured after extracting, wherein chromium (III) with DPC reaction, eliminated simultaneously Mo (VI), Cu (II), Fe (III), V (V), U (VI) and with the interference of the foreign ion such as phosphoric acid generation complex reaction.In the process of extraction, this method adds salting-out agents, accelerates extraction process, realizes the in a small amount precision measurement of uranium.This method can realize that sampling amount is the micrometric measurement of 10mg uranium content.
Description of drawings
The operational flowchart of Fig. 1 method
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail:
The method of a kind of extraction spectrophotometric method micrometric measurement uranium as shown in Figure 1, the method comprises and takes by weighing uranium sample, the uranium sample that takes by weighing is added strong phosphoric acid, potassium bichromate solution, sulfuric acid solution, sulfaminic acid solution successively stirs and carry out pre-service, adding copperas solution readjusts prices uranium (VI) to uranium (IV), then add excessive potassium dichromate, the amount of the potassium dichromate surplus that wherein adds accounts for 0.3%～0.5% of potassium dichromate total amount.By potassium dichromate U (IV) is oxidizing to U (VI), needs after the oxidation to add surfactant Tritonx-100, reach the effect of absorbance enhanced sensitivity.The chromium of organic solvent extraction surplus (VI) adopts the chromium in the spectrophotometry organic phase at last.Thereby the amount of the potassium dichromate that consumes in the time of can calculating urania (VI), thereby the micrometric measurement of realization uranium content.
The concrete operation step of this method is as follows:
Take by weighing uranium content and be about the 0.10000g uranium solution in the 250ml conical flask, add successively 40ml strong phosphoric acid, 0.2ml0.2mol/L potassium bichromate solution, 5.0ml (1: 1) sulfuric acid solution, 10ml 3mol/L sulfaminic acid solution, 5.0ml 1.0mol/L copperas solution, solution placed on the magnetic stirring apparatus stir, regulate temperature to 30～35 ℃, add 10.0ml 1% oxidizing agent solution.When solution becomes crineous, crineous is taken off in 40s.Continue to stir 2.5mins, leave standstill 30s.Then (pass through stoichiometric calculation by taking gravimetric method to add a certain amount of potassium bichromate solution, make its surplus), this method draws the excess quantity that adds potassium dichromate by test of many times and accounts for 0.3%～0.5% of potassium dichromate total amount, so just can reach the requirement of pin-point accuracy to be solved by this invention, high precision.Do not add vanadium sulfate acyl solution at uranium in U (IV) oxidation U (VI) process, broken through the constraint that adds vanadium sulfate acyl in traditional assay method, reduced the interference of vanadium sulfate acyl.
Add successively again 1.5ml 0.2%Tritonx-100 solution, 2.0ml 0.5%DPC solution, 50ml organic solvent, abundant oscillation extraction 2min, behind the standing demix 60min, aqueous phase discarded.Wherein organic solvent can adopt TBP, ethyl acetate, ether, isoamylol etc.This example preferably adopts isoamylol, and the isoamylol effect of extracting is best, and phase-splitting is fast, and the interface is clear.And in extraction process, add salting-out agents, and can accelerate extraction process like this, measure again after can placing a period of time after adopting this method extraction to finish.
Wherein, consider water and organic phase, extraction time to the impact of complex absorbance, need quantitatively to add isoamylol in this enforcement and make in the ratio 1: 2～1: 3 of organic phase and water after the extraction and the extraction time 1～3min scope extraction more complete.Preferably select and be in a ratio of 1: 3, extraction time 2min.
Adopt the chromium (VI) in the spectrophotometry organic phase, take reagent blank as reference, measure the absorbance of complex in the 546nm place with the 1cm cuvette, then find the amount (being about to uranium (IV) complete oxidation to the amount of the rear superfluous potassium dichromate of uranium (VI)) of the chromium (VI) of correspondence from working curve, thereby the amount of the potassium dichromate that consumes in the time of can calculating urania (IV), thereby the micrometric measurement of realization uranium content.
Claims (8)
1. the method for an extraction spectrophotometric method micrometric measurement uranium, comprise and take by weighing uranium sample, pre-service, readjust prices to uranium (IV), add excessive potassium dichromate to the uranium (IV) with U (IV) oxidation U (VI) described the price modification, then the chromium (VI) that adds the organic solvent extraction surplus, adopt the chromium in the spectrophotometry organic phase, it is characterized in that the excessive potassium dichromate of described adding accounts for 0.3%～0.5% of potassium dichromate total amount for the excess quantity that adds.
2. the method for a kind of extraction spectrophotometric method micrometric measurement uranium according to claim 1 is characterized in that, adds salting-out agents sodium chloride in the process of described extraction of chromium.
3. the method for a kind of extraction spectrophotometric method micrometric measurement uranium according to claim 1, it is characterized in that, add excessive potassium dichromate to the uranium (IV) and do not add vanadium sulfate acyl solution in U (IV) oxidation U (VI) process described the price modification.
4. the method for a kind of extraction spectrophotometric method micrometric measurement uranium according to claim 1 is characterized in that, the ratio of the organic phase after the described extraction of chromium and water is 1: 2～1: 3.
5. the method for a kind of extraction spectrophotometric method micrometric measurement uranium according to claim 4 is characterized in that, the ratio of the organic phase after the described extraction of chromium and water is 1: 3.
6. the method for a kind of extraction spectrophotometric method micrometric measurement uranium according to claim 1 is characterized in that, described pre-service is for adding the uranium sample that takes by weighing successively strong phosphoric acid, potassium bichromate solution, sulfuric acid solution, the stirring of sulfaminic acid solution.
7. the method for a kind of extraction spectrophotometric method micrometric measurement uranium according to claim 1, it is characterized in that described adding organic solvent extraction chromium (VI) is for adding successively behind surfactant Tritonx-100 solution, DPC solution, the organic solvent fully oscillation extraction.
8. according to claim 1 or the method for 7 described a kind of extraction spectrophotometric method micrometric measurement uranium, it is characterized in that described organic solvent is isoamylol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110097471 CN102262086B (en) | 2011-04-19 | 2011-04-19 | Method for precisely measuring uranium by extraction photometry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110097471 CN102262086B (en) | 2011-04-19 | 2011-04-19 | Method for precisely measuring uranium by extraction photometry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102262086A CN102262086A (en) | 2011-11-30 |
| CN102262086B true CN102262086B (en) | 2013-01-09 |
Family
ID=45008797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110097471 Active CN102262086B (en) | 2011-04-19 | 2011-04-19 | Method for precisely measuring uranium by extraction photometry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102262086B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103207153A (en) * | 2013-03-11 | 2013-07-17 | 中国原子能科学研究院 | Precise determination method for small amount of uranium |
| CN106932529A (en) * | 2015-12-30 | 2017-07-07 | 中核北方核燃料元件有限公司 | A kind of UO2The assay method of uranium content in-BeO pellets |
| CN107576654A (en) * | 2017-08-11 | 2018-01-12 | 泰兴协联众达化学有限公司 | A kind of test device and method of testing of phthalic anhydride total acidity |
| CN109541126A (en) * | 2018-12-19 | 2019-03-29 | 中核北方核燃料元件有限公司 | The measuring method of uranium content in a kind of U-Mo Alloy |
| CN110243778A (en) * | 2019-07-10 | 2019-09-17 | 福州大学 | The spectrophotometry of uranyl ion in a kind of measurement solution |
| CN110715922A (en) * | 2019-11-20 | 2020-01-21 | 福州大学 | Br-PADAP-uranyl ion spectrophotometry |
| CN111650142A (en) * | 2020-07-09 | 2020-09-11 | 中国原子能科学研究院 | Method for analyzing concentration of nitrous acid in uranium-containing organic phase |
-
2011
- 2011-04-19 CN CN 201110097471 patent/CN102262086B/en active Active
Non-Patent Citations (8)
| Title |
|---|
| Leonardo Sena Gomes Teixeira等.Spectrophotometric Determination of Uranium Using 2-(2-Thiazolylazo)-p-Cresol (TAC) in the Presence of Surfactants.《J. Braz. Chem. Soc.》.1999,第10卷(第6期),摘要. |
| Spectrophotometric Determination of Uranium Using 2-(2-Thiazolylazo)-p-Cresol (TAC) in the Presence of Surfactants;Leonardo Sena Gomes Teixeira等;《J. Braz. Chem. Soc.》;19991231;第10卷(第6期);摘要 * |
| 低浓度含铬废水萃取分离的研究;杜昌顺等;《北京化工大学学报》;20071231;第34卷(第2期);第115页 * |
| 刘权卫等.自动电位滴定法精密测定小量铀.《原子能科学技术》.2007,第41卷(第5期),第547页. |
| 朱海巧等.萃取光度法精密测定铀含量.《中国原子能科学研究院年报》.2008,第263-264页. |
| 杜昌顺等.低浓度含铬废水萃取分离的研究.《北京化工大学学报》.2007,第34卷(第2期),第115页. |
| 自动电位滴定法精密测定小量铀;刘权卫等;《原子能科学技术》;20070930;第41卷(第5期);第547页 * |
| 萃取光度法精密测定铀含量;朱海巧等;《中国原子能科学研究院年报》;20081231;第263-264页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102262086A (en) | 2011-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102262086B (en) | Method for precisely measuring uranium by extraction photometry | |
| CN102288600A (en) | Colorimetric measuring method for simultaneously measuring hexavalent chromium and lead | |
| CN102288725A (en) | Method for measuring organic matters in soil | |
| CN104535567A (en) | Automatic COD metering method | |
| CN108226327A (en) | LC-MS measure uranium in PUREX post processings flow 1AW, neptunium, plutonium content method | |
| CN105021545A (en) | Method for measuring contents of bismuth and lead ions in tin lead bismuth alloy electroplating solution | |
| CN103776953A (en) | Determination method of content of cobalt in lithium battery ternary positive electrode material | |
| CN102928427B (en) | Method for determining pentavalent vanadium in vanadyl sulfate | |
| CN105352900A (en) | Analysis method of chromium in chromium vanadium hydrogen storage alloy | |
| CN112710775A (en) | Method for determining content of uranium in uranium-carbon-oxygen | |
| CN103868910A (en) | Method for detecting ingredients of vanadyl sulfate product | |
| CN102323224B (en) | Methyl hydrazine analysis method | |
| CN103207153A (en) | Precise determination method for small amount of uranium | |
| CN201503398U (en) | On-line monitor for total phosphorus | |
| CN107037046B (en) | Method for analyzing content of aminohydroxyurea in nuclear fuel Purex post-treatment process | |
| CN108519374A (en) | Nuclear fuel post-processes the analysis method of hydroxy amino urea in flow | |
| CN101477057A (en) | Chemical luminescence detection method for ultra-trace reactive phosphate in sea water | |
| CN104359751A (en) | Method for determining trace uranium in soil by microwave digestion fluorescence method | |
| CN210322809U (en) | Device for analyzing and determining cyanide in water by flow injection | |
| CN107247050A (en) | The preparation of the quick detection agent of antimony and application method in a kind of measure water body | |
| CN204989129U (en) | Online electrometric titration system of totally -enclosed formula | |
| CN104597097A (en) | Method for precisely determining plutonium | |
| CN114323867A (en) | Method for analyzing and detecting uranium content in natural triuranium octoxide | |
| CN110208243B (en) | Method for simultaneously determining concentrations of uranyl nitrate and nitric acid in aqueous phase | |
| CN112630213A (en) | Chemical analysis method for detecting ceramic metallization electroplating solution |
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 |