CN106395852A - Rapid synthetic method for cheap HZSM-11 molecular sieve - Google Patents
Rapid synthetic method for cheap HZSM-11 molecular sieve Download PDFInfo
- Publication number
- CN106395852A CN106395852A CN201610417336.7A CN201610417336A CN106395852A CN 106395852 A CN106395852 A CN 106395852A CN 201610417336 A CN201610417336 A CN 201610417336A CN 106395852 A CN106395852 A CN 106395852A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- hzsm
- cheap
- synthesis method
- crystallization
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention specifically relates to a rapid synthetic method for a cheap HZSM-11 molecular sieve, belonging to the technical field of synthesis of molecular sieves. The rapid synthetic method comprises the following steps: successively adding water, an alkali source, a template, a silicon source and an aluminum source; carrying out uniform mixing under stirring so as to form initial gel; then adding a guiding agent, carrying out uniform mixing under stirring and then placing the obtained mixture into a reaction vessel for crystallization; and after crystallization, subjecting a product to washing, drying and roasting successively so as to obtain the HZSM-11 molecular sieve. Through addition of the guiding agent, crystallization time is substantially shortened, and the crystallinity degree of a ZSM-11 molecular sieve is increased; the HZSM-11 molecular sieve is synthesized in one step without usage of a sodium-containing raw material, subsequent ammonium exchange process is avoided, yield is substantially improved, and the preparation cost of the molecular sieve is substantially reduced; and the preparation method is simple to operate and convenient for industrialization.
Description
Technical field
The invention belongs to Zeolite synthesis technical field is and in particular to a kind of fast synthesis method of cheap HZSM-11 molecular sieve.
Background technology
Silicon-oxy tetrahedron in Pentasil framework of molecular sieve is linked into special construction unit, and it is made up of 8 five-membered rings, this
Structure is connected to chain by common edge, and then is linked to be laminated structure again, using different on-link mode (OLM) (symmetrical centre related and
Minute surface is related) two kinds of node configurations of MFI and MEL can be respectively obtained.Pentasil molecular sieve is elementary composition and have difference according to it
Title, wherein, sial type is referred to as ZSM-5 (MFI) and ZSM-11 (MEL), total silicon type referred to as silicalite-1 (MFI) and
Silicalite-2 (MEL), titanium silicon type is commonly called as TS-1 (MFI) and TS-2 (MEL).
ZSM-11 molecular sieve is a kind of new structure molecule being developed at first in phase early 1970s by Mobil company
Sieve.It is applied to a lot of petrochemical catalysts as catalytic active component at present, for example, be hydrocracked and catalytic dewaxing catalyst
In.By NaZSM-11 exchange system for HZSM-11, complex operation.The system of existing synthesis ZSM-11 molecular sieve can contain
Alkali metal cation, the presence of these ions increased the post-processing difficulty of molecular sieve, increases the manufacturing cost of molecular sieve.
The synthetic method of ZSM-11 molecular sieve has many kinds at present, how using traditional hydrothermal synthesis method.For example, patent US
6444191 do template, 140～200 DEG C of crystallization temperature with 3,5-N, N- parvoline, and crystallization time is 2～20 days；Specially
Sharp CN102557071A is with four butyl bromation amine as template, bivalence alkali metal hydroxide as alkali source, crystallization temperature 60～
120 DEG C, crystallization time is 24～48 hours；Using the synthesis of low-temperature hydrothermal crystallization method, (tide ZSM-11 divides such as Guo Xinwen etc.
Son sieve low temperature synthesis and sign. Journal of Dalian University of Technology Total, 2001,41 (4):426～430) Ludox or white carbon, hydroxide are adopted
Sodium, TBAH are raw material, at 60 DEG C, crystallization 8d～16d；It is required to longer crystallization time in said method,
And be required for carrying out ion exchange.
Content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of no sodium system of cheap high-crystallinity ZSM-11 molecular sieve
Preparation Method.The introducing of directed agents not only effectively shortens crystallization time, and in TBABr-NH3The molecular sieve knot of synthesis under system
Brilliant degree is high, substantially increases product yield, significantly reduces the preparation cost of molecular sieve.
The purpose of the present invention is achieved by below scheme：
Sequentially add water, alkali source, template, silicon source, silicon source, stir formation Primogel, is eventually adding directed agents and stirs
It is placed in crystallization in reactor after mixing uniformly, after crystallization terminates, product is washed, is dried, roasting is obtained HZSM-11 molecular sieve.
Described template is tetrabutyl ammonium bromide.
Described silicon source is selected from one of aluminum sulfate, aluminum nitrate, boehmite or several.
Described silicon source be selected from Ludox, white carbon, c-type silica gel or tetraethyl orthosilicate one or several.
Described alkali source is ammonia.
The mol ratio of described formation Primogel is：SiO2:Al2O3:Template:NH3:H2O=1:0.01～0.03:0.01～
0.1:10～30:40～90.
The preparation method of described directed agents is as follows：
It is directed to agent silicon source, directed agents silicon source, directed agents alkali source, template, water according to SiO2:Al2O3:Template:
NH3:H2O=1:0.01～0.03:0.01～0.1:20～25:After 10～40 proportioning mixing and stirring, by mixture 120～
Crystallization 3～12h at 180 DEG C, prepared directed agents.
Described directed agents addition is Primogel butt quality 2～10%.
Described crystallization temperature is 120～180 DEG C, and crystallization time is 12～48h.
Described baking temperature is 110～120 DEG C, and drying time is 6～12h；Sintering temperature is 500～600 DEG C, during roasting
Between be 5h.
In sum, the present invention has advantages below：
(1) addition of directed agents not only substantially reduces crystallization time, and improves the degree of crystallinity of ZSM-11 molecular sieve.
(2) it is provided without containing sodium raw materials, one-step synthesis go out Hydrogen ZSM-11 molecular formula, it is to avoid follow-up ammonium exchange process, significantly
Improve yield, greatly reduce the preparation cost of molecular sieve.
(3) present invention is easy and simple to handle, is conducive to industrialization.
Brief description
Fig. 1 is X-ray diffraction (XRD) spectrogram going out HZSM-11 sieve sample synthesized by comparative example 1.
Fig. 2 is X-ray diffraction (XRD) spectrogram going out high-crystallinity HZSM-11 sieve sample synthesized by embodiment 1.
Fig. 3 is X-ray diffraction (XRD) spectrogram going out high-crystallinity HZSM-11 sieve sample synthesized by embodiment 2.
Fig. 4 is X-ray diffraction (XRD) spectrogram going out high-crystallinity HZSM-11 sieve sample synthesized by embodiment 3.
Specific embodiment
With reference to embodiment, the present invention will be further described.
In order that those skilled in the art are better understood from the present invention, below in conjunction with specific embodiment, the present invention is done further
Bright, but protection domain not thereby limiting the invention.
Gained sieve sample relative crystallinity is with 2 θ in synthesis of molecular sieve ZSM-11 sieve sample spectrogram at 22.5～25.0 °
Between two peak-to-peak area sums ratio, and using molecular sieve in following embodiments 1 as standard specimen.
Comparative example 1
The preparation of directed agents：According to synthesis mol ratio SiO2:Al2O3:TBA+:NH3:H2O=1:0.015:0.01:25:40 mixing,
Mixture crystallization 12h at 120 DEG C is obtained directed agents；
According to synthesis mol ratio SiO2:Al2O3:TBABr:Na2O:H2O=1:0.015:0.22:0.23:25, successively by deionized water,
Liquid caustic soda (NaOH 47.8wt%), tetrabutylammonium hydrogen ammonium bromide (100wt%) stir, white carbon (SiO288.6wt%) (plus
The white carbon consumption entering is 0.1 mole, and in embodiment, the consumption of each raw material all adds according to aforementioned proportion), add after stirring
Enter boehmite solid (Al2O365wt%), it is eventually adding directed agents, the consumption of directed agents is Primogel butt quality 2%,
Put into after stirring in reactor in 170 DEG C of crystallization 72 hours, be down to room temperature, filtering and washing, to neutral, dries 12 for 120 DEG C
Hour, 550 DEG C of roastings 5 hours, prepared pure phase NaZSM-11 molecular sieve powder.The relative crystallinity that this method is made is 100%.
Embodiment 1
The preparation of directed agents：According to synthesis mol ratio SiO2:Al2O3:TBA+:NH3:H2O=1:0.02:0.1:20:20 mixing, mix
Compound crystallization 3h at 180 DEG C is obtained directed agents；
According to synthesis mol ratio SiO2:Al2O3:TBABr:NH3:H2O=1:0.01:0.1:10:40, successively by deionized water, ammonia
(NH3Wt25%), tetrabutylammonium hydrogen ammonium bromide (100wt%) stir, Ludox (SiO225wt%) (silicon of addition is molten
Glue consumption is 0.1 mole, and in embodiment, the consumption of each raw material all adds according to aforementioned proportion), it is stirring evenly and then adding into aluminum sulfate
Solution (Al2O37.13wt%), it is eventually adding directed agents, the consumption of directed agents is Primogel butt quality 2%, stirs
After put in reactor in 120 DEG C of crystallization 48 hours, be down to room temperature, filtering and washing to neutral, dries 12 hours for 120 DEG C, 550 DEG C
Roasting 5 hours, prepared pure phase HZSM-11 molecular sieve powder.The relative crystallinity that this method is made is 104%.
Embodiment 2
The preparation of directed agents：According to synthesis mol ratio SiO2:Al2O3:TBA+:NH3:H2O=1:0.03:0.1:25:35 mixing, mix
Compound crystallization 6h at 150 DEG C is obtained directed agents；
According to synthesis mol ratio SiO2:Al2O3:TBABr:NH3:H2O=1:0.03:0.01:30:90, successively by deionized water, ammonia
Water (NH3Wt25%), tetrabutylammonium hydrogen ammonium bromide (100wt%) stir, c-type silica gel (SiO290.2wt%) (add
C-type silica gel consumption be 0.1 mole, in embodiment the consumption of each raw material all according to aforementioned proportion add), after stirring plus
Enter aluminum nitrate solution (Al2O310.2wt%), it is eventually adding directed agents, the consumption of directed agents is Primogel butt quality 10%,
Put into after stirring in reactor in 180 DEG C of crystallization 12 hours, be down to room temperature, filtering and washing, to neutral, dries 12 for 120 DEG C
Hour, 550 DEG C of roastings 5 hours, prepared pure phase HZSM-11 molecular sieve powder.The relative crystallinity that this method is made is 114%.
Embodiment 3
The preparation of directed agents：According to synthesis mol ratio SiO2:Al2O3:TBA+:NH3:H2O=1:0.025:0.07:23:10 mixing,
Mixture crystallization 10h at 135 DEG C is obtained directed agents；
According to synthesis mol ratio SiO2:Al2O3:TBABr:NH3:H2O=1:0.02:0.0.05:20:63, successively by deionized water, ammonia
Water (NH3Wt25%), tetrabutylammonium hydrogen ammonium bromide (100wt%) stir, tetraethyl orthosilicate (SiO228wt%) (add
Tetraethyl orthosilicate consumption be 0.1 mole, in embodiment the consumption of each raw material all according to aforementioned proportion add), after stirring
Add aluminum sulfate (Al2O37.13wt%), it is eventually adding directed agents, the consumption of directed agents is Primogel butt quality 6%, stirs
Mix and put into after uniformly in reactor in 150 DEG C of crystallization 36 hours, be down to room temperature, to neutral, 120 DEG C to dry 12 little for filtering and washing
When, 550 DEG C of roastings 5 hours, prepared pure phase HZSM-11 molecular sieve powder.The relative crystallinity that this method is made is 116%.
Claims (10)
1. a kind of fast synthesis method of cheap HZSM-11 molecular sieve is it is characterised in that comprise the following steps：Sequentially add water,
Alkali source, template, silicon source, silicon source, stir formation Primogel, is eventually adding after directed agents stir and is placed in reaction
Crystallization in kettle, after crystallization terminates, product is washed, is dried, roasting is obtained HZSM-11 molecular sieve.
2. cheap high-crystallinity HZSM-11 molecular sieve according to claim 1 fast synthesis method it is characterised in that
Described template is tetrabutyl ammonium bromide.
3. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described aluminum
Source is selected from one of aluminum sulfate, aluminum nitrate, boehmite or several.
4. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described silicon
Source be selected from Ludox, white carbon, c-type silica gel or tetraethyl orthosilicate one or several.
5. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described alkali
Source is ammonia.
6. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described shape
Become Primogel mol ratio be：SiO2:Al2O3:Template:NH3:H2O=1:0.01～0.03:0.01～0.1:10～30:40～
90.
7. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described leads
As follows to the preparation method of agent：
It is directed to agent silicon source, directed agents silicon source, directed agents alkali source, template, water according to SiO2:Al2O3:Template:
NH3:H2O=1:0.01～0.03:0.01～0.1:20～25:After 10～40 proportioning mixing and stirring, by mixture 120～
Crystallization 3～12h at 180 DEG C, prepared directed agents.
8. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described leads
It is Primogel butt quality 2～10% to agent addition.
9. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described crystalline substance
Changing temperature is 120～180 DEG C, and crystallization time is 12～48h.
10. the fast synthesis method of cheap HZSM-11 molecular sieve according to claim 1 is it is characterised in that described is dry
Dry temperature is 110～120 DEG C, and drying time is 6～12h；Sintering temperature is 500～600 DEG C, and roasting time is 5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610417336.7A CN106395852A (en) | 2016-06-15 | 2016-06-15 | Rapid synthetic method for cheap HZSM-11 molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610417336.7A CN106395852A (en) | 2016-06-15 | 2016-06-15 | Rapid synthetic method for cheap HZSM-11 molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106395852A true CN106395852A (en) | 2017-02-15 |
Family
ID=58006563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610417336.7A Pending CN106395852A (en) | 2016-06-15 | 2016-06-15 | Rapid synthetic method for cheap HZSM-11 molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106395852A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107262144A (en) * | 2017-06-20 | 2017-10-20 | 中国华电集团科学技术研究总院有限公司 | Applied to distributed busbar protection internal combustion engine fume high-temperature denitrating catalyst |
| CN110203946A (en) * | 2019-05-30 | 2019-09-06 | 中国科学院大连化学物理研究所 | A kind of synthetic method of little crystal grain MEL Si-Al molecular sieve material |
| CN113753912A (en) * | 2020-06-03 | 2021-12-07 | 中国石油天然气股份有限公司 | ZSM-11 molecular sieve and synthesis method thereof |
| CN116099570A (en) * | 2021-11-10 | 2023-05-12 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN116174023A (en) * | 2021-11-29 | 2023-05-30 | 中国石油天然气股份有限公司 | Preparation method of high-yield high-octane gasoline additive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468808A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing phosphorous ZSM-5 molecular sieve |
| CN102897788A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Synthesis method for ZSM-11 molecular sieve |
| CN103086399A (en) * | 2011-10-31 | 2013-05-08 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
-
2016
- 2016-06-15 CN CN201610417336.7A patent/CN106395852A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468808A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing phosphorous ZSM-5 molecular sieve |
| CN102897788A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Synthesis method for ZSM-11 molecular sieve |
| CN103086399A (en) * | 2011-10-31 | 2013-05-08 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107262144A (en) * | 2017-06-20 | 2017-10-20 | 中国华电集团科学技术研究总院有限公司 | Applied to distributed busbar protection internal combustion engine fume high-temperature denitrating catalyst |
| CN110203946A (en) * | 2019-05-30 | 2019-09-06 | 中国科学院大连化学物理研究所 | A kind of synthetic method of little crystal grain MEL Si-Al molecular sieve material |
| CN110203946B (en) * | 2019-05-30 | 2022-12-13 | 中国科学院大连化学物理研究所 | Synthesis method of small-grain MEL silicon-aluminum molecular sieve material |
| CN113753912A (en) * | 2020-06-03 | 2021-12-07 | 中国石油天然气股份有限公司 | ZSM-11 molecular sieve and synthesis method thereof |
| CN113753912B (en) * | 2020-06-03 | 2023-05-26 | 中国石油天然气股份有限公司 | ZSM-11 molecular sieve and synthesis method thereof |
| CN116099570A (en) * | 2021-11-10 | 2023-05-12 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN116174023A (en) * | 2021-11-29 | 2023-05-30 | 中国石油天然气股份有限公司 | Preparation method of high-yield high-octane gasoline additive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106395852A (en) | Rapid synthetic method for cheap HZSM-11 molecular sieve | |
| CN102502687A (en) | Method for greenly synthesizing Ti-Si molecular sieve | |
| CN103964462B (en) | The method of microwave solid source Fast back-projection algorithm zeolite molecular sieve | |
| CN103708496B (en) | A kind of HZSM-5@silicalite-1 nucleocapsid structure molecular sieve and preparation method thereof and application | |
| CN103896303A (en) | Method for directly synthesizing high silica-alumina ratio ultrafine NaY molecular sieve | |
| CN105000571B (en) | A kind of coexisting molecular sieves of EU 1/ZSM 48 and its preparation and application | |
| CN106276948B (en) | A kind of Ti-beta molecular sieve and its synthetic method and application | |
| CN110342535A (en) | A kind of preparation method for the porous HZSM-5 zeolite molecular sieve that soda acid is modified | |
| CN107662927A (en) | A kind of method that NaY molecular sieve is prepared using Si-Al molecular sieve crystallization mother liquor | |
| CN102040229A (en) | Synthetic method of MCM-22 (Multiple Chip Module 22) molecular sieve | |
| US10287172B2 (en) | Preparation method for beta zeolite | |
| CN114436279B (en) | ZSM-22 molecular sieve, preparation method and application thereof, and n-dodecane isomerization reaction | |
| CN106745053A (en) | Microwave synthesizes the method for high selectivity preparing propylene from methanol molecular sieve of Nano zeolite | |
| CN106082262A (en) | The preparation method of Hydrogen ZSM 11 molecular sieve | |
| CN108439427A (en) | A kind of method that fabricated in situ is rich in mesoporous NaY molecular sieve | |
| CN107162013B (en) | A kind of synthetic method of TS-1 Titanium Sieve Molecular Sieve | |
| CN105712374B (en) | A kind of preparation method of hollow USY molecular sieve | |
| CN102897788B (en) | Synthesis method for ZSM-11 molecular sieve | |
| CN105776242A (en) | Synthesis method of ZSM-50 molecular sieve | |
| CN105460951B (en) | The synthetic method of high silica alumina ratio Y zeolites | |
| CN106430236A (en) | Preparation method for mesoporous ZSM-5 molecular sieve | |
| CN106276955B (en) | A kind of Ti-beta molecular sieves and its synthetic method and application | |
| CN106276954B (en) | A kind of Ti-beta molecular sieves and its preparation method and application | |
| CN106082259A (en) | There is overlength catalytic life HTS and low cost preparation method thereof | |
| CN103818922A (en) | Method for synthesizing UZM-8 molecular sieve through microwave heating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170215 |
|
| RJ01 | Rejection of invention patent application after publication |