CN108607554B - RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method thereof - Google Patents
RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method thereof Download PDFInfo
- Publication number
- CN108607554B CN108607554B CN201810395260.1A CN201810395260A CN108607554B CN 108607554 B CN108607554 B CN 108607554B CN 201810395260 A CN201810395260 A CN 201810395260A CN 108607554 B CN108607554 B CN 108607554B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrazine hydrate
- produce hydrogen
- rhcr
- soluble
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and a preparation method thereof. The catalyst is prepared by adopting a one-step reduction method, sodium borohydride is taken as a reducing agent, and sodium borohydride is also taken as a reducing agentThe mixed solution of the original Rh source and the Cr source precursor. The catalyst shows excellent catalytic performance on decomposition of hydrazine hydrate to produce hydrogen under 323K, the hydrogen selectivity of the reaction reaches 100%, and the conversion frequency (TOF) value is as high as 500(mol H)2mol metal‑1h‑1). The method for preparing the catalyst is simple and convenient to operate, and the obtained catalyst has the characteristics of small particle size, large specific surface area, more catalytic active sites and the like, has high catalytic activity and stability, and is a catalyst with great development prospect.
Description
Technical Field
The invention relates to a RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and a preparation method thereof, belonging to the field of hydrogen storage materials.
Background
Energy is an important strategic material developed by the state. The basic trend of global energy transformation is to realize the transformation from fossil energy systems (such as petroleum, natural gas, coal and the like) to low-carbon energy systems, and finally enter a sustainable energy era mainly based on renewable energy. Among the various alternative energy sources, hydrogen energy has the characteristics of reproducibility, no pollution, high combustion value, easiness in storage and transportation and the like, and is known as the next-generation secondary clean energy source. The industrial chain with complete hydrogen energy mainly comprises links of large-scale preparation, storage, transportation, application and the like of the hydrogen energy, wherein a safe and efficient hydrogen storage technology is a key and is a bottleneck technology for development of the hydrogen energy at present. Nitrogen-based hydrides have attracted a great deal of interest to researchers because of their high hydrogen content, high hydrogen storage density, and their significant advantages in terms of hydrogen release performance.
Hydrazine (N)2H4) The hydrogen content is up to 12.5 wt%, and the completely decomposed product is H2And N2Is a hydrogen source with application prospect. However, hydrazine is extremely toxic, and is easy to explode when contacting with a metal catalyst, so that certain potential safety hazards exist. However, when hydrazine forms hydrazine hydrate (N) with water2H4·H2O), the properties become more stable and still contain hydrogen mass fractions of up to 8.0 wt%, and thus are more suitable for research as hydrogen source. The water molecules in hydrazine hydrate do not participate in the reaction, and the products of complete decomposition and hydrazineThe same as (reaction 1). However, there is also a competitive side reaction pathway (reaction 2) in which H reacts when a side reaction occurs2The selectivity is greatly reduced. Therefore, the development of a high-efficiency and stable hydrogen production catalyst is the key to the research of using hydrazine hydrate as a hydrogen storage material.
N2H4→N2+2H2(1)
3N2H4→4NH3+N2(2)
In 2009, the xu professor research group of japan institute of industrial and technology integration prepared a series of transition metal single-component nanoparticles using a liquid phase reduction method, in which Rh nanoparticles showed the optimal catalytic activity, but H was H2The selectivity is only 44% (J.Am.chem.Soc.2009,131, 9894-9895). At present, the catalyst for catalyzing hydrazine hydrate to completely decompose and produce hydrogen is mainly concentrated in Ni-based noble metal alloy nano materials, such as Pt-Ni, Rh-Ni, Pd-Ni and the like. The hydrazine hydrate decomposition hydrogen production generally has the problems of low catalyst activity and low recycling stability. Therefore, the development of a novel efficient and stable catalyst has certain scientific significance in catalyzing hydrazine hydrate to completely produce hydrogen.
Disclosure of Invention
The invention aims to provide a RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen is obtained by directly reducing mixed solution of Rh source and Cr source precursor by using sodium borohydride as a reducing agent under 298K.
A preparation method of a RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen comprises the following steps:
(1) forming a mixed solution by using a soluble Rh source precursor and a soluble Cr source precursor;
(2) and (2) adding a sodium borohydride solution into the mixed solution obtained in the step (1), and reacting for a period of time to obtain the RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen.
Preferably, the soluble Rh source precursor is rhodium trichloride, rhodium triiodide, rhodium nitrate or ammonium chlororhodate.
Preferably, the soluble Cr source precursor is chromium nitrate, sodium chromate, potassium chromate, or ammonium chromate.
Preferably, the molar ratio (n) of the soluble Rh source precursor to the soluble Cr source precursor isRh/nCr) Is 0.11 to 9.0.
Preferably, the concentration of the sodium borohydride solution is 0.8-1.6 mol/L.
Preferably, the reaction in step (2) is carried out at 298K under vigorous stirring for 30 minutes.
When the method is implemented, the method can be operated according to the following steps:
(1) adding a soluble Rh source precursor into ultrapure water, and uniformly stirring;
(2) adding a soluble Cr source precursor into the step (1), and uniformly stirring;
(3) and (3) adding a sodium borohydride solution into the mixed solution obtained in the step (2), and vigorously stirring and reducing for 30 minutes at 298K to obtain the RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen.
The RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen is a black powdery amorphous substance and can be used for catalyzing the decomposition of hydrazine hydrate to produce hydrogen after the decomposition of hydrazine hydrate.
The invention has the beneficial effects that: according to TEM, SAED and EDS characterization analysis, the RhCr catalyst for hydrogen production by hydrazine hydrate decomposition has the characteristics of about 4.2nm in particle size, small particles, many catalytic active sites and the like. Obtaining Rh and Cr when the molar ratio of the metal Rh to Cr is 7:3 by a catalytic hydrazine hydrate decomposition hydrogen production test0.7Cr0.3The catalyst has optimal catalytic effect, efficiently catalyzes hydrazine hydrate to decompose and produce hydrogen under 323K alkaline environment, the selectivity of the hydrogen reaches 100 percent, and the conversion frequency (TOF) value is as high as 500(mol H)2mol metal-1h-1) Moreover, the catalyst has better recycling stability for decomposing hydrazine hydrate to produce hydrogen, and the activity and the gas yield of the catalyst are not reduced after the catalyst is repeatedly used for 5 timesThe catalyst has better catalytic activity and cycle stability.
Drawings
FIG. 1 shows Rh obtained in example 1 of the present invention0.7Cr0.3Transmission electron micrographs of the catalyst;
FIG. 2 shows Rh obtained in example 1 of the present invention0.7Cr0.3A selected area electron diffraction pattern of the catalyst;
FIG. 3 shows Rh obtained in example 1 of the present invention0.7Cr0.3EDS energy spectrum of the catalyst;
FIG. 4 is a graph of the amount of gas produced by the decomposition of hydrazine hydrate catalyzed at 323K by RhCr catalysts of varying Rh to Cr molar ratios obtained in examples 1 and 8-11 of the present invention versus time;
FIG. 5 shows Rh obtained in example 1 of the present invention0.7Cr0.3A cyclic use performance test chart of the catalyst for catalyzing hydrazine hydrate to decompose and produce hydrogen under 323K.
Detailed Description
Example 1:
1) adding 0.07mol of rhodium trichloride into 5ml of ultrapure water, and uniformly stirring;
2) adding 0.03mol of chromium nitrate into the mixture obtained in the step 1), and uniformly stirring;
3) adding 1mL of 0.8mol/L sodium borohydride solution into the mixed solution obtained in the step 2), and stirring and reducing for 30 minutes to obtain a metal component Rh0.7Cr0.3A catalyst.
Example 2:
the rhodium trichloride in the step 1) in the embodiment 1 is changed into rhodium triiodide, and other steps are the same as the step 1, so that the metal component obtained is Rh0.7Cr0.3A catalyst.
Example 3:
the rhodium trichloride in the step 1) in the embodiment 1 is changed into rhodium nitrate, and other steps are the same as the step 1, so that the metal component obtained is Rh0.7Cr0.3A catalyst.
Example 4:
the rhodium trichloride in the step 1) in the embodiment 1 is changed into ammonium chlororhodate, and other steps are the same as the step 1, so that the metal component obtained is Rh0.7Cr0.3A catalyst.
Example 5:
the chromium nitrate in the step 2) of the example 1 is changed into sodium chromate, and other steps are the same as the example 1 to obtain the chromium nitrate with the metal component Rh0.7Cr0.3A catalyst.
Example 6:
the chromium nitrate in the step 2) of the example 1 is changed into potassium chromate, and other steps are the same as the example 1, so that the metal component Rh is obtained0.7Cr0.3A catalyst.
Example 7:
the chromium nitrate obtained in step 2) of example 1 was changed to ammonium chromate, and the other steps were the same as those of example 1 to obtain a chromium nitrate alloy having a metal component Rh0.7Cr0.3A catalyst.
Example 8:
the dosage of rhodium trichloride in the step 1) in the embodiment 1 is changed to 0.01mmol, the dosage of chromium nitrate in the step 2) is changed to 0.09mmol, and other steps are the same as the embodiment 1, so that the obtained metal component is Rh0.1Cr0.9A catalyst.
Example 9:
the dosage of rhodium trichloride in the step 1) in the embodiment 1 is changed to 0.03mol, the dosage of chromium nitrate in the step 2) is changed to 0.07mmol, and other steps are the same as the embodiment 1, so that the obtained metal component is Rh0.3Cr0.7A catalyst.
Example 10:
the dosage of rhodium trichloride in the step 1) in the embodiment 1 is changed to 0.05mol, the dosage of chromium nitrate in the step 2) is changed to 0.05mol, and other steps are the same as the embodiment 1, so that the obtained metal component is Rh0.5Cr0.5A catalyst.
Example 11:
the dosage of rhodium trichloride in the step 1) in the embodiment 1 is changed to 0.09mol, the dosage of chromium nitrate in the step 2) is changed to 0.01mmol, and other steps are the same as the embodiment 1, so that the obtained metal component is Rh0.9Cr0.1A catalyst.
Example 12:
the concentration of sodium borohydride in step 3) of example 1 was changed to 1.0mol/mL, and other steps were performed in the same manner as described aboveExample 1 obtaining a Metal component Rh0.7Cr0.3A catalyst.
Example 13:
the concentration of sodium borohydride in the step 3) in the example 1 is changed to 1.2mol/mL, and other steps are the same as the example 1 to obtain the metal component Rh0.7Cr0.3A catalyst.
Example 14:
the concentration of sodium borohydride in the step 3) in the example 1 is changed to 1.4mol/mL, and other steps are the same as the example 1 to obtain the metal component Rh0.7Cr0.3A catalyst.
Example 15:
the concentration of sodium borohydride in the step 3) in the example 1 is changed to 1.6mol/mL, and other steps are the same as the example 1 to obtain the metal component Rh0.7Cr0.3A catalyst.
Examples 16 to 20:
hydrazine hydrate (N) is catalyzed by the RhCr catalysts prepared in examples 1, 8, 9, 10 and 112H4·H2O) hydrogen production (16, 17, 18, 19 and 20), placing the catalyst into a 50ml two-neck flask containing 5ml of ultrapure water, adding 416mg of NaOH, and then adding 1mmol of hydrazine hydrate into the reaction system by using a liquid transfer gun. The reaction was carried out at 323K (hydrogen generation diagram is shown in FIG. 4), and the following results were obtained (Table I). From the first Table, it can be found that Rh was present when the molar ratio of metallic Rh to metallic Cr was 2.330.7Cr0.3The catalyst has optimal catalytic effect, and only 2.40min is needed for catalyzing the hydrazine hydrate to be completely decomposed to produce hydrogen.
Example 21:
with Rh obtained in example 10.7Cr0.3The catalyst is subjected to a cyclic performance test, after hydrazine hydrate is decomposed to produce hydrogen, the same amount of hydrazine hydrate is added into a two-neck flask to test Rh0.7Cr0.3The recycling performance of the catalyst for catalyzing the decomposition of hydrazine hydrate to produce hydrogen is shown in figure 5 in detail. Multiple cyclesTests show that the synthesized Rh0.7Cr0.3The catalyst has good recycling performance.
According to TEM, SAED and EDS characterization analysis, the RhCr catalyst has the characteristics of about 4.2nm in particle size, small particles, more catalytic active sites and the like. Obtaining Rh when the molar ratio of metal Rh to Cr is 2.33 by a catalytic hydrazine hydrate decomposition hydrogen production test0.7Cr0.3The catalyst has optimal catalytic effect, efficiently catalyzes hydrazine hydrate to decompose and produce hydrogen under 323K alkaline environment, the selectivity of the hydrogen reaches 100 percent, and the conversion frequency (TOF) value is as high as 500(mol H)2mol metal-1h-1) And the catalyst has better recycling stability for decomposing hydrazine hydrate to produce hydrogen, and the activity and gas yield of the catalyst are not reduced after the catalyst is repeatedly used for 5 times, which shows that the catalyst has better catalytic activity and recycling stability.
In conclusion, the method for preparing the catalyst is simple and convenient to operate, and the obtained catalyst has the characteristics of small particle size, large specific surface area, many catalytic active sites and the like, has high catalytic activity and stability, and is a catalyst with great development prospect.
Claims (5)
1. A preparation method of RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen is characterized in that the catalyst is a black powdery amorphous substance, and the method comprises the following steps:
(1) forming a mixed solution by using a soluble Rh source precursor and a soluble Cr source precursor;
(2) adding a sodium borohydride solution into the mixed solution obtained in the step (1), and reacting for a period of time to obtain the RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen;
the molar ratio of the soluble Rh source precursor to the soluble Cr source precursor is 7: 3;
the concentration of the sodium borohydride solution is 0.8-1.6 mol/L;
the reaction in the step (2) is carried out at the temperature of 298K under the condition of vigorous stirring, and the reaction time is 30 minutes.
2. The method of claim 1, wherein the soluble Rh source precursor is rhodium trichloride, rhodium triiodide, rhodium nitrate, or ammonium chlororhodate.
3. The method of claim 1, wherein the soluble Cr source precursor is chromium nitrate, sodium chromate, potassium chromate, or ammonium chromate.
4. The RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen, which is prepared according to the method of any one of claims 1 to 3.
5. Use of a RhCr catalyst for the decomposition of hydrazine hydrate to produce hydrogen according to claim 4, characterized in that it is used to catalyze the decomposition of hydrazine hydrate to produce hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810395260.1A CN108607554B (en) | 2018-04-27 | 2018-04-27 | RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810395260.1A CN108607554B (en) | 2018-04-27 | 2018-04-27 | RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108607554A CN108607554A (en) | 2018-10-02 |
| CN108607554B true CN108607554B (en) | 2020-03-13 |
Family
ID=63661370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810395260.1A Active CN108607554B (en) | 2018-04-27 | 2018-04-27 | RhCr catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108607554B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631932B (en) * | 2011-02-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof |
-
2018
- 2018-04-27 CN CN201810395260.1A patent/CN108607554B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108607554A (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Air-engaged fabrication of nitrogen-doped carbon skeleton as an excellent platform for ultrafine well-dispersed RuNi alloy nanoparticles toward efficient hydrolysis of ammonia borane | |
| Xu et al. | Boron doping and high curvature in Bi nanorolls for promoting photoelectrochemical nitrogen fixation | |
| Kaya | Evaluating organic waste sources (spent coffee ground) as metal-free catalyst for hydrogen generation by the methanolysis of sodium borohydride | |
| Zhang et al. | Recent advances in application of graphitic carbon nitride‐based catalysts for photocatalytic nitrogen fixation | |
| Demirci et al. | Kinetics of Ru-promoted sulphated zirconia catalysed hydrogen generation by hydrolysis of sodium tetrahydroborate | |
| Yue et al. | Recent advance in heterogenous electrocatalysts for highly selective nitrite reduction to ammonia under ambient condition | |
| CN103949272B (en) | NiPt@RGO composite nano catalyst for producing hydrogen by using hydrazine borane and preparation method thereof | |
| CN110433796B (en) | Preparation method and application of noble metal nanoparticles with stable graphene quantum dots | |
| CN101428756A (en) | Automatic hydrogen production method by using hydroboron composition | |
| Lu et al. | Kinetic and mechanistic analysis of NH 3 decomposition on Ru (0001), Ru (111) and Ir (111) surfaces | |
| Yuan et al. | Cation/anion-doping induced electronic structure regulation strategy to boost the catalytic hydrogen evolution from ammonia borane hydrolysis | |
| Duan et al. | Pd-Co2P nanoparticles supported on N-doped biomass-based carbon microsheet with excellent catalytic performance for hydrogen evolution from formic acid | |
| Qin et al. | Electrochemical NO3–reduction catalyzed by atomically precise Ag30Pd4 bimetallic nanocluster: synergistic catalysis or tandem catalysis? | |
| Liu et al. | Catkin-derived mesoporous carbon-supported molybdenum disulfide and nickel hydroxyl oxide hybrid as a bifunctional electrocatalyst for driving overall water splitting | |
| CN110368999B (en) | Catalyst, preparation method and application thereof | |
| CN113522263B (en) | Preparation method and application of phosphorus-doped graphene-loaded nickel-platinum nano-catalyst | |
| Guo et al. | Surface property and spatial confinement engineering for achieving Ru nanoclusters on O/N-doped hollow carbon towards enhanced hydrogen production | |
| Gao et al. | Thermodynamic and kinetic considerations of nitrogen carriers for chemical looping ammonia synthesis | |
| Wang et al. | Self-supported Cu (OH) 2@ Co2CO3 (OH) 2 core–shell nanowire array as a robust catalyst for ammonia-borane hydrolysis | |
| Yuan et al. | Photo/electrochemical Urea Synthesis via CO2 Coupling with Nitrogenous Small Molecules: Status and Challenges for the Development of Mechanism and Catalysts | |
| Zhang et al. | Recent advances in the catalytic conversion of CO2 to chemicals and demonstration projects in China | |
| Zhang et al. | Construction of graphdiyne (CnH2n-2) based Co-SP/CuI double S-scheme heterojunctions proved with in situ XPS characterization for efficient photocatalytic hydrogen production | |
| CN106861708B (en) | A kind of non-precious metal catalyst and preparation method thereof producing hydrogen completely for hydrazine borine | |
| CN110404558B (en) | NiPt-Ni (OH) for hydrogen production by hydrazine decomposition 2 /La(OH) 3 Catalyst and preparation method thereof | |
| Zhang et al. | Recent advances in multilevel nickel-nitrogen-carbon catalysts for CO2electroreduction to CO |
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 |