CN105271283A - Preparing method for pinnoite - Google Patents
Preparing method for pinnoite Download PDFInfo
- Publication number
- CN105271283A CN105271283A CN201510813150.9A CN201510813150A CN105271283A CN 105271283 A CN105271283 A CN 105271283A CN 201510813150 A CN201510813150 A CN 201510813150A CN 105271283 A CN105271283 A CN 105271283A
- Authority
- CN
- China
- Prior art keywords
- boron
- pinnoite
- rich
- old halogen
- rich old
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention belongs to the technical field of borate preparation and particularly discloses a preparing method for pinnoite. The method comprises the steps that A, boron-rich old brine is heated at constant temperature until crystals are dissolved out, wherein the mass percentage of B2O3 in boron-rich old brine is not smaller than 1%, and the temperature for constant temperature heating ranges from 60 DEG C to100 DEG C; B, boron-rich old brine with the crystals dissolved out is aged at constant temperature, solid-liquid separation is carried out to obtain filter cake and filter liquor, and the filter cake is washed and dried to obtain pinnoite, wherein the temperature for constant temperature aging is the same as that for constant temperature heating. According to the preparing method for pinnoite, boron-rich old brine is used as a raw material, pinnoite is obtained through one-step method, and the problem that due to the solid-liquid-solid conversion process, the product morphology is poor is avoided; the preparing method is easy to operate, external reagent does not need to be added, and the raw materials are low in price and easy to obtain; synthesized pinnoite is high in purity, good in morphology and uniform in granularity distribution, and is a good nonlinear optical material.
Description
Technical field
The invention belongs to borate preparing technical field, specifically, relate to a kind of preparation method of pinnoite.
Background technology
Boratory structure-rich is colorful, and it is by sp
2hybridized orbital or sp
3hybridized orbital becomes key formation more to enrich and the various borates of complexity compared with silicate sturcture; Because borate structure species is various, complicated various, therefore borate has unique physicochemical property, and as premium propertiess such as fire-retardant, heat-resisting, wear-resistant, anticorrosion and optically nonlinearities, it has a wide range of applications in fields such as national defence, metallurgy, medicine, building and electron trades.Pinnoite (MgOB
2o
33H
2o) be dibasic magnesium borate, having non-centrosymmetric structure, is a kind of non-linear optic crystal, has stronger thermoelectricity, piezoelectricity and non-linear optical effect, is a kind of potential nonlinear optical material.
At present, synthesis about pinnoite is mainly prepared by indirect methods such as two step synthesis: one is obtained by being dissolved in by hungchaoite in boiling boric acid aqueous solution, another kind is by separating out Phase transformation in magnesium sulfate salt lake brine, then to be dissolved in by Phase transformation in 60 DEG C of water or to be dissolved in 30 DEG C of massfractions be obtained in the magnesium chloride solution of 2% ~ 13%.Solid above two kinds of methods all have employed solid-liquid-the indirect preparative column szaibelyite of transform mode; The former need prepare hungchaoite by magnesium oxide, but the pinnoite product of this method synthesis is simultaneously containing sheet (granularity is little) and column two kinds of patterns, and size-grade distribution is uneven, directly affects quality product.And first the latter will prepare Phase transformation, then be raw material with Phase transformation, this raw material not easily prepares, and generated time is longer, generally can reach some months even six months, the more important thing is that its building-up process is comparatively complicated.
Summary of the invention
For solving above-mentioned prior art Problems existing, the invention provides a kind of preparation method of pinnoite, this preparation method for raw material, obtains pinnoite by controlling thermostat temperature and can growing through ageing with boron-rich old halogen; This preparation method is simple, and the pinnoite product pattern of synthesis is better, purity is higher.
In order to reach foregoing invention object, present invention employs following technical scheme:
A preparation method for pinnoite, comprises step: A, by boron-rich old halogen thermostatically heating until there is crystal to separate out; Wherein, B in described boron-rich old halogen
2o
3mass percent be not less than 1%; The temperature range of described thermostatically heating is 60 DEG C ~ 100 DEG C; B, will have the boron-rich old halogen constant temperature ageing that crystal separates out, and solid-liquid separation obtains filter cake and filtrate, and described filter cake obtains pinnoite through washing, drying; Wherein, the temperature of described constant temperature ageing is identical with the temperature of described thermostatically heating.
Further, before by described boron-rich old halogen heating, also step is comprised: in described boron-rich old halogen, add deionized water dilute.
Further, when by described boron-rich old halogen dilution, the mass ratio of described deionized water and boron-rich old halogen is no more than 1:10.
Further, the source of described boron-rich old halogen is the magnesium sulfate salt lake brine of boracic.
Further, in described step B, described in have the digestion time of boron-rich old halogen that crystal separates out be 4d ~ 60d.
Further, in described step B, described in have the digestion time of boron-rich old halogen that crystal separates out be 7d ~ 50d.
Further, described thermostatically heating and constant temperature ageing are carried out in water-bath.
Further, B in described boron-rich old halogen
2o
3mass percent be 2% ~ 5%.
Further, the temperature range of the thermostatically heating of described boron-rich old halogen is 60 DEG C ~ 80 DEG C.
The present invention for raw material, has namely prepared pinnoite by single stage method with boron-rich old halogen; Compared to existing technology with hungchaoite or Phase transformation for prepared by raw material, direct is that solid phase obtains target product pinnoite by liquid-phase conversion, Gu thus avoid the poor problem of product pattern that solid-liquid-conversion process causes, and this preparation method is simple to operate, without the need to adding any external agent, cheaper starting materials is easy to get; The pinnoite purity of synthesis is high, pattern good, even particle size distribution, is a kind of good nonlinear optical material.
Accompanying drawing explanation
The following description carried out in conjunction with the drawings, the above-mentioned and other side of embodiments of the invention, feature and advantage will become clearly, in accompanying drawing:
Fig. 1 is the XRD photo of the pinnoite according to embodiments of the invention 1;
Fig. 2 is the SEM photo of the pinnoite according to embodiments of the invention 1;
Fig. 3 is the optical performance test result of the pinnoite according to embodiments of the invention 2.
Embodiment
Below, embodiments of the invention are described in detail with reference to the accompanying drawings.But, the present invention can be implemented in many different forms, and the present invention should not be interpreted as being limited to the specific embodiment of setting forth here.On the contrary, provide these embodiments to be to explain principle of the present invention and practical application thereof, thus enable others skilled in the art understand various embodiment of the present invention and be suitable for the various amendments of certain expected application.
Embodiment 1
Preparation method according to the pinnoite of embodiments of the invention 1 comprises the steps:
Step one, adds deionized water and dilutes, obtain boron-rich dilution bittern in boron-rich old halogen; Particularly, in described boron-rich dilution bittern, the mass ratio of boron-rich old halogen and deionized water is 2:1.
In the present embodiment, this boron-rich old halogen is from the magnesium sulfate salt lake brine of boracic, and wherein magnesium chloride is saturated; The component concentration of magnesium sulfate salt lake brine with reference to " analytical procedure of bittern and salt " (analyzer room of Qinghai Yanhu Inst., Chinese Academy of Sciences. the analytical procedure [M] of bittern and salt. Beijing: Science Press, 1988:3-9) described in.
Carried out chemical composition total analysis to the boron-rich old halogen in the present embodiment, analytical results is as shown in table 1.
The boron-rich old halogen chemical composition total analysis result of table 1
| Chemical composition | Na + | Mg 2+ | K + | Li + | B 2O 3 | Cl - | SO 4 2- |
| Mass percentage/% | -0.038 | 8.782 | 0.059 | 0.268 | 2.930 | 23.665 | 2.474 |
It will be appreciated by those skilled in the art that in Table 1, Na
+content analysis is generally calculated by minusing, and therefore there will be negative value situation as described in table 1, above-mentioned situation all belongs in limit of error; Hereafter in like manner.
Step 2, seals boron-rich dilution bittern and is placed in the water bath with thermostatic control of 80 DEG C, until crystal is separated out.
In the present embodiment, first boron-rich dilution bittern is sealed to prevent from causing evaporation in 80 DEG C of thermostatic processes, thus produce impurity; And when boron-rich dilution bittern is placed in 80 DEG C of water bath with thermostatic control about 5d, namely this boron-rich dilution bittern start to become muddy, and produce unformed floss; That is, start have crystal to separate out gradually.
Step 3, keeps 80 DEG C of constant temperature ageing 7d, and carries out solid-liquid separation, obtain filter cake and filtrate, and filter cake obtains pinnoite through washing, drying.
Particularly, filter cake can adopt distilled water wash once, absolute ethanol washing once, and dries under room temperature (about 25 DEG C).
X-ray diffraction (being called for short XRD), scanning electron microscope (being called for short SEM) and thermogravimetric analysis are carried out respectively to the pinnoite prepared through above-mentioned steps one to step 3, has carried out chemical analysis simultaneously.Chemical analysis solid-phase component is: 24.37%MgO and 42.31%B
2o
3, compare the theoretical value of the two in pinnoite and be respectively 24.58%MgO and 42.46%B
2o
3, difference is less; Be 33.16% in conjunction with thermogravimetric dehydration result, 32.96% difference comparing theoretical thermogravimetric dehydration is also less simultaneously; Illustrate that the purity of the pinnoite of synthesis is higher; More than be mass percent.The XRD photo of the pinnoite that the present embodiment prepares and SEM photo are respectively as shown in Figure 1, 2; As can be seen from Figure 1, this spectrogram peak shape is sharp-pointed, baseline is level and smooth, without assorted peak etc., also show pinnoite that the present embodiment prepares not only better crystallinity degree and purity is higher, impure hardly; As can be seen from Figure 2, the pinnoite pattern of the present embodiment synthesis is better, in column, and even particle size distribution.
Embodiment 2
In the description of embodiment 2, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 2 is, to the operation that boron-rich old halogen dilutes in removal step one with the difference of embodiment 1; In step 2, get boron-rich old halogen and seal and be placed in the water bath with thermostatic control of 60 DEG C, until crystal is separated out.
In the present embodiment, this boron-rich old halogen is from the magnesium sulfate salt lake brine of boracic, and wherein magnesium chloride is saturated; Carried out chemical composition total analysis to the boron-rich old halogen in the present embodiment, analytical results is as shown in table 2.
The boron-rich old halogen chemical composition total analysis result of table 2
| Chemical composition | Na + | Mg 2+ | K + | Li + | B 2O 3 | Cl - | SO 4 2- |
| Mass percentage/% | 0.800 | 8.705 | 0.075 | 0.298 | 4.556 | 23.671 | 3.018 |
The boron-rich old halogen that the present embodiment adopts reacts about 10d in water bath with thermostatic control at 60 DEG C, namely starts to occur muddiness, and produces unformed floss; That is, start have crystal to separate out.
In step 3, keep 60 DEG C of constant temperature ageing 30d, carry out solid-liquid separation, obtain filter cake and filtrate, filter cake obtains pinnoite through washing, drying.
Particularly, filter cake can adopt distilled water wash once, absolute ethanol washing three times, and to dry under room temperature (about 25 DEG C).
Adopt UV-Vis DRS (UV-visspectrometer) optical property to the pinnoite prepared through above-mentioned steps one to step 3 to test, test result as shown in Figure 3.As can be seen from Figure 3, the hydroxyl peak of wavelength to be 1000nm place be pinnoite; At visible region (400nm ~ 800nm), the transmittance of this pinnoite is higher; Its reflectivity reaches more than 65% at 200nm place; Showing that the pinnoite prepared in the present embodiment has ultraviolet or deep ultraviolet nonlinear characteristic thus, is a kind of potential nonlinear optical material.
Embodiment 3
In the description of embodiment 3, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 3 is with the difference of embodiment 1, and in step one, in described boron-rich dilution bittern, the mass ratio of boron-rich old halogen and deionized water is 1:10; And the chemical composition total analysis result of boron-rich old halogen in the present embodiment is as shown in table 3.
The boron-rich old halogen chemical composition total analysis result of table 3
| Chemical composition | Na + | Mg 2+ | K + | Li + | B 2O 3 | Cl - | SO 4 2- |
| Mass percentage/% | -0.025 | 8.542 | 0.068 | 0.341 | 4.665 | 21.786 | 3.418 |
In step 2, namely described boron-rich dilution bittern start to become muddy after being placed in the water bath with thermostatic control 1d of 60 DEG C, occurs unformed floss, shows to start have crystal to separate out; In step 3, keep 60 DEG C of constant temperature ageing 50d, through solid-liquid separation, filter cake through distilled water wash once, absolute ethanol washing three times, room temperature (about 25 DEG C) dry and namely obtain pinnoite.
Embodiment 4
In the description of embodiment 4, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 4 is, to the operation that boron-rich old halogen dilutes in removal step one with the difference of embodiment 1; In step 2, described boron-rich old halogen reacts about 11d in water bath with thermostatic control at 80 DEG C, namely starts to occur muddiness, and produces unformed floss; That is, start have crystal to separate out; In step 3, keep 80 DEG C of constant temperature ageing 5d, carry out solid-liquid separation, obtain filter cake and filtrate, filter cake obtains pinnoite through washing, drying.
Embodiment 5
In the description of embodiment 5, do not repeat them here with the something in common of embodiment 1, only describe the difference with embodiment 1.Embodiment 5 is with the difference of embodiment 1, to the operation of boron-rich old halogen dilution in removal step one; In the present embodiment, the chemical composition total analysis result of boron-rich old halogen is see in embodiment 3 shown in table 3; In step 2, described boron-rich old halogen reacts about 25d in water bath with thermostatic control at 60 DEG C, namely starts to occur muddiness, and produces unformed floss; That is, start have crystal to separate out; In step 3, keep 60 DEG C of constant temperature ageing 15d, carry out solid-liquid separation, obtain filter cake and filtrate, filter cake through distilled water wash once, absolute ethanol washing three times, room temperature (about 25 DEG C) dry and namely obtain the higher pinnoite of purity.
What deserves to be explained is, in the preparation method of pinnoite according to the present invention, the Heating temperature of boron-rich old halogen (or through diluting the boron-rich dilution bittern obtained) is not limited to 60 DEG C and 80 DEG C in above-described embodiment 1-5, and general control can prepare pinnoite in the scope of 60 DEG C ~ 100 DEG C.Meanwhile, the object of ageing process be to remove contain in precipitating crystalline impurity, precipitating crystalline is grown increase crystal particle diameter and crystal particle diameter is evenly distributed, therefore digestion time is also not limited to 7d, 30d, 50d, 5d and the 15d described in above-described embodiment 1-5.Generally according to the content of each ion in the boron-rich old halogen of raw material (or through diluting the boron-rich dilution bittern obtained), the purity that digestion time controls can prepare at 4d ~ 60d is high, pattern good, the pinnoite of even particle size distribution.And in the process that boron-rich old halogen (or through diluting the boron-rich dilution bittern obtained) is heated, also be not limited to adopt the water-bath in above-described embodiment, other are as heating means such as oil baths, react under remaining on fixed temperature to make above-mentioned reaction system.
By comparative example 1 and embodiment 4, can find out, separated out for the crystal in the step 2 in above-mentioned two embodiments, obviously short compared with in embodiment 4 in embodiment 1 time, and in the digestion time embodiment 1 in step 3 compared with obviously will grow in embodiment 4; Equally, also there is above-mentioned phenomenon in comparing embodiment 3 and embodiment 5, and it is shorter that crystal namely in embodiment 3 time of separating out separates out the time compared with the crystal in embodiment 5, and digestion time in embodiment 3 is longer compared with the digestion time in embodiment 5; Therefore say, in the preparation process being raw material with boron-rich dilution bittern, there is dilution salify phenomenon, dilution can promote formation and the precipitation of pinnoite; But meanwhile, due to the shorter precipitation time, cause generating a large amount of unformed pinnoites, it needs to be converted into pinnoite crystal through ageing; And dilution to a certain degree can cause the pH of reaction system to increase, be unfavorable for the conversion of crystal, therefore, also can affect digestion time by boron-rich old halogen to the dilution of boron-rich dilution bittern, and extension rate is larger, digestion time will be longer.
The preparation method of pinnoite according to an embodiment of the invention, for raw material, has namely prepared pinnoite by single stage method with boron-rich old halogen (or through diluting the boron-rich dilution bittern obtained); Compared to existing technology with hungchaoite or Phase transformation for prepared by raw material, direct is that solid phase obtains target product pinnoite by liquid-phase conversion, Gu thus avoid the poor problem of product pattern that solid-liquid-conversion process causes, and this preparation method is simple to operate, without the need to adding any external agent, cheaper starting materials is easy to get; The pinnoite purity of synthesis is high, pattern good, even particle size distribution, is a kind of good nonlinear optical material.
Illustrate and describing the present invention with reference to specific embodiment, but it should be appreciated by those skilled in the art that: when not departing from the spirit and scope of the present invention by claim and equivalents thereof, the various changes in form and details can be carried out at this.
Claims (9)
1. a preparation method for pinnoite, is characterized in that, comprises step:
A, by boron-rich old halogen thermostatically heating until there is crystal to separate out; Wherein, B in described boron-rich old halogen
2o
3mass percent be not less than 1%; The temperature range of described thermostatically heating is 60 DEG C ~ 100 DEG C;
B, will have the boron-rich old halogen constant temperature ageing that crystal separates out, and solid-liquid separation obtains filter cake and filtrate, and described filter cake obtains pinnoite through washing, drying; Wherein, the temperature of described constant temperature ageing is identical with the temperature of described thermostatically heating.
2. the preparation method of pinnoite according to claim 1, is characterized in that, before by described boron-rich old halogen heating, also comprises step: in described boron-rich old halogen, add deionized water dilute.
3. the preparation method of pinnoite according to claim 2, is characterized in that, when by described boron-rich old halogen dilution, the mass ratio of described deionized water and boron-rich old halogen is no more than 1:10.
4., according to the preparation method of the arbitrary described pinnoite of claim 1-3, it is characterized in that, the source of described boron-rich old halogen is the magnesium sulfate salt lake brine of boracic.
5. the preparation method of pinnoite according to claim 4, is characterized in that, in described step B, described in have the digestion time of boron-rich old halogen that crystal separates out be 4d ~ 60d.
6. the preparation method of pinnoite according to claim 5, is characterized in that, in described step B, described in have the digestion time of boron-rich old halogen that crystal separates out be 7d ~ 50d.
7. the preparation method of pinnoite according to claim 6, is characterized in that, described thermostatically heating and constant temperature ageing are carried out in water-bath.
8. the preparation method of pinnoite according to claim 1, is characterized in that, B in described boron-rich old halogen
2o
3mass percent be 2% ~ 5%.
9. the preparation method of pinnoite according to claim 1, is characterized in that, the temperature range of the thermostatically heating of described boron-rich old halogen is 60 DEG C ~ 80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510813150.9A CN105271283B (en) | 2015-11-19 | 2015-11-19 | The preparation method of pinnoite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510813150.9A CN105271283B (en) | 2015-11-19 | 2015-11-19 | The preparation method of pinnoite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105271283A true CN105271283A (en) | 2016-01-27 |
| CN105271283B CN105271283B (en) | 2017-06-20 |
Family
ID=55141222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510813150.9A Active CN105271283B (en) | 2015-11-19 | 2015-11-19 | The preparation method of pinnoite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105271283B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079362A (en) * | 2019-06-14 | 2020-12-15 | 中国科学院青海盐湖研究所 | Preparation method of polyboromagnesite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256242A (en) * | 1999-12-23 | 2000-06-14 | 化学工业部天津化工研究设计院 | Production process of boric acid and magnesium carbonate from boromagnesite |
| CN103303935A (en) * | 2013-06-21 | 2013-09-18 | 赵传立 | Method for producing boric acids with lean pinnoite ores |
| CN104803400A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院过程工程研究所 | Ammonium magnesium sulfate preparation method |
-
2015
- 2015-11-19 CN CN201510813150.9A patent/CN105271283B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256242A (en) * | 1999-12-23 | 2000-06-14 | 化学工业部天津化工研究设计院 | Production process of boric acid and magnesium carbonate from boromagnesite |
| CN103303935A (en) * | 2013-06-21 | 2013-09-18 | 赵传立 | Method for producing boric acids with lean pinnoite ores |
| CN104803400A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院过程工程研究所 | Ammonium magnesium sulfate preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079362A (en) * | 2019-06-14 | 2020-12-15 | 中国科学院青海盐湖研究所 | Preparation method of polyboromagnesite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105271283B (en) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mackinnon et al. | Hydrothermal syntheses of zeolite N from kaolin | |
| CN108529652B (en) | Resource utilization process of industrial sodium chloride | |
| WO2018041272A1 (en) | Method for preparing industrial grade lithium carbonate from crude lithium fluoride, and a lithium carbonate product | |
| Li et al. | Concentration variation of aluminate ions during the seeded precipitation process of gibbsite from sodium aluminate solution | |
| CN104445411B (en) | A kind of preparation method of macrobead molybdic acid | |
| Trypuć et al. | CaCO3 production using liquid waste from Solvay method | |
| CN108751242A (en) | A kind of low sodium alumina decomposition technique and low sodium alumina | |
| CN108285152A (en) | A kind of green high-efficient synthetic method of Copper-cladding Aluminum Bar SBA-15 meso-porous molecular sieve materials | |
| CN105271283A (en) | Preparing method for pinnoite | |
| CN109208077B (en) | Monofluorophosphate as one kind of non-linear optical crystal | |
| US1504669A (en) | Titanium compound | |
| KR950004771B1 (en) | Method for production of mixed ammonium-rare earth osalates and rare earth oxides so produced | |
| CN109721082A (en) | A kind of production method of high purity magnesium hydroxide and potassium nitrate coproduction | |
| EP0012488B1 (en) | Process for the preparation of calcium sulphate hemihydrate and calcium sulphate hemihydrate obtained by this process | |
| Akhtar et al. | Chemical modulation of crystalline state of calcium oxalate with nickel ions | |
| CN111039325B (en) | Continuous evaporation crystallization method of sodium molybdate dihydrate | |
| BR102014009507A2 (en) | boussingaultite production process from liquid effluents containing magnesium sulphate | |
| WO2022257240A1 (en) | Niobium-doped alpo-31 molecular sieve crystal and preparation method therefor | |
| US1937956A (en) | Process of making potassium aluminum fluoride | |
| CN106146285A (en) | A kind of sulphuric acid hydrolysis prepares the method for gallic acid | |
| CN115417433B (en) | Method for producing high-purity sodium nitrate | |
| CN110871094A (en) | Mn-doped sodium nickel phosphate photocatalytic material and preparation method thereof | |
| US3480388A (en) | Preparation of hydrargillite crystals | |
| CN108083328B (en) | A kind of single-phase metatitanic acid samarium nano-powder and method of solwution method preparation | |
| RU2630493C1 (en) | Method for producing nitrogen-potassium sulfate fertiliser and hydrochloric acid |
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 |