CN104785287A - Modification method for improving stability of catalyst in catalytic pyrolysis of biomass - Google Patents
Modification method for improving stability of catalyst in catalytic pyrolysis of biomass Download PDFInfo
- Publication number
- CN104785287A CN104785287A CN201510119924.8A CN201510119924A CN104785287A CN 104785287 A CN104785287 A CN 104785287A CN 201510119924 A CN201510119924 A CN 201510119924A CN 104785287 A CN104785287 A CN 104785287A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- biomass
- hzsm
- catalytic pyrolysis
- temperature
- 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
Abstract
The invention discloses a modification method for improving stability of a catalyst in catalytic pyrolysis of biomass; the modification method includes the following steps: mixing evenly a silicon-containing organic compound and an organic solvent, to prepare a silicon-containing organic solution, then placing an HZSM-5 catalyst in the silicon-containing organic solution, and stirring for 0.5-12 h at the temperature of 20-100 DEG C, wherein the mass ratio of the silicon-containing organic solution to the HZSM-5 catalyst according to the mass of silicon dioxide is 1:100 to 20:100; followed by, evaporating at the temperature of 80-90 DEG C to make a residue sticky; drying the residue for 2-3 h at the temperature of 80-90 DEG C, then drying for 2-3 h at the temperature of 100-120 DEG C, and cooling; and next, carrying out constant temperature calcination for 5-10 h at the temperature of 500-700 DEG C, cooling, and then sieving to obtain a modified HZSM-5 catalyst. The method adjusts and changes acid sites on the external surface of the catalyst and modifies catalyst pore passages, and the stability of the catalyst is improved.
Description
Technical field
The invention belongs to biomass conversion preparing liquid fuel and chemical products field, particularly a kind of method of modifying for improving catalyst stability in catalytic pyrolysis of biomass.
Background technology
The total energy consumption in the whole world progressively increases, the key factor having become restriction global economic development in short supply of fossil energy resource, the CO of release when fossil energy consumes simultaneously
2gas causes greenhouse effects, SO
2and the environmental problem serious threat that causes of nitrogen oxide is economical and the sustainable development of society.Therefore, greatly develop new and renewable sources of energy, realize energy-saving and emission-reduction and low-carbon economy becomes particularly important.
Biomass energy is a kind of form of energy be stored in the form of chemical energy by solar energy in bio-carrier.The amount of the carbon dioxide of discharge when the carbon dioxide absorbed in biomass growth process is equivalent to utilize, the clean discharge capacity of carbon dioxide is approximately zero, can not aggravate greenhouse effects.Current China biomass utilization technologies is varied, can be divided into Direct-Combustion Technology, biochemical transformation technology and thermochemical study technology.Wherein thermochemical study technology comprises gasification and pyrolysis liquefaction technology, can be liquid fuel-bio oil by biomass conversion by biomass pyrolytic technology, thus petroleum replacing resource, not only can alleviate China's energy starved present situation, all right decreasing pollution, improves the ecological environment.
Biomass pyrolytic efficiently can prepare bio oil, but the shortcoming such as the bio oil obtained has that oxygen content is high, moisture is high, acidity is high and thermal instability is strong, the high-grade that can not realize oil substitutes.Current quality of bio-oil lift technique is the emphasis of research both at home and abroad, and catalytic pyrolysis of biomass directly utilizes technology as a kind of living beings, can carry out under normal pressure, middle temperature, realizes the once conversion from living beings to liquid fuel.But this technology has the shortcoming of the low and easy coking and deactivation of catalyst of target product productive rate at present.In order to improve Product yields in biomass pyrolytic, find excellent catalyst, and then improve catalyst anticoking capability, and increase the productive rate of target product.HZSM-5 molecular sieve catalyst is owing to having special pore passage structure, and the aromatisation of high specific surface area and excellence, isomerization and alkylation performance (shape selective catalysis performance), have critical role in catalytic pyrolysis of biomass application.But the macromolecular compound that biomass pyrolytic produces is easy at HZSM-5 catalyst external surface polymerization coking, thus blocking catalyst aperture, hinder pyrogenic steam to enter inside, duct, make its active reduction until inactivation.
Summary of the invention
The object of the invention is to provide a kind of method of modifying for improving catalyst stability in catalytic pyrolysis of biomass, and regulating catalyst outer surface acid site modified catalyst duct, improves catalyst stability.
The present invention is by the following technical solutions:
For improving a method of modifying for catalyst stability in catalytic pyrolysis of biomass, comprise the steps:
Step one, siliceous organic matter and organic solvent mixed be mixed with siliceous organic solution, again HZSM-5 catalyst is placed in siliceous organic solution, 0.5 ~ 12h is stirred at 20 ~ 100 DEG C, wherein, siliceous organic solution in the mass ratio of the quality of silica and HZSM-5 catalyst for 1:100 ~ 20:100;
Step 2, at 80 ~ 90 DEG C, be evaporated to residue thickness afterwards, by residue dry 2 ~ 3h at 80 ~ 90 DEG C, then at 100 ~ 120 DEG C dry 2 ~ 3h, cooling;
Step 3, afterwards calcining at constant temperature 5 ~ 10h at 500 ~ 700 DEG C, sieve after cooling and obtain modified HZSM-5 catalyst.
Siliceous organic matter described in step one comprises gamma-aminopropyl-triethoxy-silane (KH550), ethyl orthosilicate (TEOS) or methyl-silicone oil, and described organic solvent comprises n-hexane.The speed of described stirring is 1000 ~ 3000r/min, is controlled the amount of siliceous organic solution during stirring by condensing reflux.
The heating rate of calcining at constant temperature described in step 3 is 8 ~ 12 DEG C/min.
Beneficial effect of the present invention:
Modified HZSM-5 catalyst of the present invention is that siliceous for large molecule organic matter is deposited on catalyst external surface by chemical liquid deposition (CLD), then calcine and siliceous organic matter is converted into silica inert substance covers catalyst external surface, can catalyst external surface acid site, cover part modified catalyst duct.So compared with unmodified catalyst, catalyst external surface acid site is reduced, after polymerization habituation, and the coking rate of catalyst obviously declines, and the method is conducive to the stability improving catalyst in biomass pyrolytic, and obtains the liquid fuel of more high-quality.Catalyst preparation process is simple, has good application prospect.
Accompanying drawing explanation
Fig. 1 is that the catalyst furans of different modifier modification transforms hydro carbons each product carbon productive rate, corresponding catalyst modification operating mode: SiO
2deposition is 4%, the CLD processing time be 6h, CLD treatment temperature is 20 DEG C.
Fig. 2 is that the catalyst furans of different silica deposit amount modification transforms each product carbon productive rate, and corresponding catalyst modification operating mode: KH550 is modifier, CLD processing time 6h, CLD treatment temperature 20 DEG C.
Fig. 3 is that the catalyst furans of different liquid deposition processing time modification transforms each product carbon productive rate, corresponding catalyst modification operating mode: SiO
2deposition 4%, KH550 is modifier, and CLD treatment temperature is 20 DEG C.
Fig. 4 is that the catalyst furans of different liquid deposition treatment temperature modification transforms each product carbon productive rate, and corresponding catalyst modification operating mode: KH550 is modifier, SiO
2deposition is 4%, CLD processing time 6h.
Fig. 5 is the relative peak area ratio of the catalyst pine sawdust converted product of different silica deposit amount modification, and corresponding catalyst modification operating mode: KH550 is modifier, CLD processing time 6h, CLD treatment temperature 20 DEG C.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing the present invention done and further explain.The following example only for illustration of the present invention, but is not used for limiting practical range of the present invention.
For improving a method of modifying for catalyst stability in catalytic pyrolysis of biomass, comprise the steps:
Step one, siliceous organic matter and organic solvent mixed be mixed with siliceous organic solution, again HZSM-5 catalyst is placed in siliceous organic solution, 0.5 ~ 12h is stirred with 1000 ~ 3000r/min at 20 ~ 100 DEG C, controlled the amount of siliceous organic solution by condensing reflux during stirring, wherein, described siliceous organic matter comprises KH550, TEOS or methyl-silicone oil; Described organic solvent comprises n-hexane; Siliceous organic solution in the mass ratio of the quality of silica and HZSM-5 catalyst for 1:100 ~ 20:100;
Step 2, afterwards at 80 ~ 90 DEG C rotate be evaporated to residue thickness; By residue dry 2 ~ 3h at 80 ~ 90 DEG C, then at 100 ~ 120 DEG C dry 2 ~ 3h, cooling;
Step 3, be that 8 ~ 12 DEG C/min is warming up to 500 ~ 700 DEG C and carries out calcining at constant temperature 5 ~ 10h with heating rate afterwards, cross 40 ~ 70 object sieves after cooling and obtain modified HZSM-5 catalyst.
SiO described in the present invention
2deposition refers to the SiO that catalyst surface deposits
2quality accounts for the percentage of catalyst (unmodified) quality.
Embodiment 1
KH550 is joined in n-hexane, mix and be mixed with the solution that concentration is 0.0667mol/L, get this solution of 100ml and put into conical flask, add 10gHZSM-5 catalyst (namely silica deposit amount is 4%) again, conical flask is placed in water-bath, bath temperature controls at 20 DEG C, and connects reflux, and whole process is with 2000r/min magnetic agitation 6h; After 6h, the mixture in conical flask is transferred in evaporative flask, and connects rotary evaporation instrument apparatus, by n-hexane solvent evaporate to dryness at 85 DEG C; By the fraction collection in evaporative flask in a Noah's ark, dry 2h in the baking oven of 85 DEG C, then in the baking oven of 110 DEG C dry 2h, take out after cooling, be placed in the Muffle furnace of 600 DEG C and calcine 6h, take out after cooling, cross Collection and conservation after 50 object sieves.
The performance test of catalyst: using furans as the representative of biomass derivatives, carries out catalyzed conversion to it on a fixed bed, pyrolysis temperature 600 DEG C, mass space velocity 1.5h
-1, carrier gas N
2flow velocity 200ml/min, reaction result is shown in Fig. 1.
Embodiment 2
Preparation method is identical with embodiment 1, and difference is that TEOS is replaced KH550, and concentration is 0.0667mol/L (namely silica settling amount is 4%).The performance test conditions of catalyst is with embodiment 1, and reaction result is shown in Fig. 1.
Embodiment 3
Preparation method is identical with embodiment 1, and difference is that methyl-silicone oil is replaced KH550, and concentration is 0.0667mol/L (namely silica deposit amount is 4%).The performance test conditions of catalyst is with embodiment 1, and reaction result is shown in Fig. 1.
Comparative example
Do not carry out modification to HZSM-5 catalyst, directly carry out the performance test of catalyst, test condition is with embodiment 1, and reaction result is shown in Fig. 1.
As can be seen from Figure 1, KH550 is that the catalyst surface coking rate that modifier obtains is minimum, and the productive rate of alkene and aromatic hydrocarbon is the highest.
Embodiment 4
Preparation method is identical with embodiment 1, and difference is that KH550 to be mixed with respectively concentration be 0.0167mol/L, 0.03335mol/L, 0.133mol/L, 0.267mol/L (namely silica deposit amount is respectively 1%, 2%, 8%, 16%).The performance test conditions of catalyst is with embodiment 1, and reaction result is shown in Fig. 2.
As can be seen from Figure 2, SiO
2deposition directly affects catalyst surface acid site degree of passivation and aperture degree of modification, take KH550 as modifier, and when silica deposit amount is 4%, modified catalyst surface coking rate is minimum, drops to 26.7% by 44.1% during unmodified catalyst; Work as SiO
2when deposition is 8%, in furans pyrolysis alkene and aromatic hydrocarbon productive rate maximum, be elevated to 17.2%, 25.6% by 9.8% during unmodified catalyst, 18.8% respectively.
Embodiment 5
Preparation method is identical with embodiment 1, difference be respectively 0 the magnetic agitation time, 1,3,12h (namely the CLD processing time be respectively 0,1,3,12h).The performance test conditions of catalyst is with embodiment 1, and reaction result is shown in Fig. 3.
As can be seen from Figure 3, along with the prolongation in CLD processing time, catalyst surface coking rate first declines with the CLD processing time and tends towards stability afterwards, and the productive rate of alkene and aromatic hydrocarbon is increased to stable gradually.
Embodiment 6
Preparation method is identical with embodiment 1, and difference is that magnetic agitation temperature is respectively 50 DEG C and 90 DEG C (namely CLD treatment temperature is respectively 50 DEG C and 90 DEG C).The performance test conditions of catalyst is with embodiment 1, and reaction result is shown in Fig. 4.
As can be seen from Figure 4, from the angle of catalyst surface coking rate, when CLD treatment temperature is 20 DEG C, modified ZSM-5 catalyst anticoking capability is better, and coking rate is reduced to 26.7% by 44.1% of untreated ZSM-5 catalyst; When CLD treatment temperature is 50 DEG C, the productive rate of alkene and aromatic hydrocarbon is larger, 18.7%, 27.3% is increased to by 9.8%, 18.8% of untreated catalyst, when CLD treatment temperature is elevated to 90 DEG C, the productive rate of alkene and aromatic hydrocarbon declines to a great extent, and its value is lower than productive rate during CLD treatment temperature 20 DEG C.
From operation ease and modified catalyst catalytic performance in general, the optimum operating condition of CLD modified ZSM-5 catalyst is: take KH550 as modifier, SiO
2deposition is that 4%, CLD processing time and temperature are respectively 6h and 20 DEG C.
Embodiment 7
Using pine sawdust as raw material, Py-GC/MS device carries out catalytic pyrolysis test.Get 0.5mg pine sawdust in quartz ampoule, fix at pine sawdust two ends with a small amount of silica wool, the catalyst in each weighing 1mg embodiment 4 in quartz ampoule one end, and is fixed with silica wool, and namely pine sawdust and catalyst quality are than being 1:4, and thermal cracking temperature is 600 DEG C.As shown in Figure 5, the relative area of benzene,toluene,xylene and indenes first raises rear decline than the increase with silica deposit amount to arene peak areas ratio, and the relative area of naphthalene reduces than relative, and less with the variation tendency of silica deposit amount.When silica deposit amount is 4%, the relative area of benzene,toluene,xylene is than the highest.
Claims (4)
1. for improving a method of modifying for catalyst stability in catalytic pyrolysis of biomass, it is characterized in that, comprising the steps:
Step one, siliceous organic matter and organic solvent mixed be mixed with siliceous organic solution, again HZSM-5 catalyst is placed in siliceous organic solution, 0.5 ~ 12h is stirred at 20 ~ 100 DEG C, wherein, siliceous organic solution in the mass ratio of the quality of silica and HZSM-5 catalyst for 1:100 ~ 20:100;
Step 2, at 80 ~ 90 DEG C, be evaporated to residue thickness afterwards, by residue dry 2 ~ 3h at 80 ~ 90 DEG C, then at 100 ~ 120 DEG C dry 2 ~ 3h, cooling;
Step 3, afterwards calcining at constant temperature 5 ~ 10h at 500 ~ 700 DEG C, sieve after cooling and obtain modified HZSM-5 catalyst.
2. the method for modifying for improving catalyst stability in catalytic pyrolysis of biomass according to claim 1, it is characterized in that, described in step one, siliceous organic matter comprises gamma-aminopropyl-triethoxy-silane, ethyl orthosilicate or methyl-silicone oil, and described organic solvent comprises n-hexane.
3. the method for modifying for improving catalyst stability in catalytic pyrolysis of biomass according to claim 1, is characterized in that, the speed stirred described in step one is 1000 ~ 3000r/min, is controlled the amount of siliceous organic solution during stirring by condensing reflux.
4. the method for modifying for improving catalyst stability in catalytic pyrolysis of biomass according to claim 1, is characterized in that, the heating rate of calcining at constant temperature described in step 3 is 8 ~ 12 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510119924.8A CN104785287A (en) | 2015-03-18 | 2015-03-18 | Modification method for improving stability of catalyst in catalytic pyrolysis of biomass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510119924.8A CN104785287A (en) | 2015-03-18 | 2015-03-18 | Modification method for improving stability of catalyst in catalytic pyrolysis of biomass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104785287A true CN104785287A (en) | 2015-07-22 |
Family
ID=53550742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510119924.8A Pending CN104785287A (en) | 2015-03-18 | 2015-03-18 | Modification method for improving stability of catalyst in catalytic pyrolysis of biomass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104785287A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126901A (en) * | 2015-09-14 | 2015-12-09 | 青岛大学 | Molecular sieve catalyst applied to seaweed liquefaction reaction and preparation method thereof |
| CN106732754A (en) * | 2017-01-23 | 2017-05-31 | 东南大学 | The sour dealuminzation method for preparing catalyst of hydro carbons yield is improved for biomass pyrolytic |
| CN108774538A (en) * | 2018-05-04 | 2018-11-09 | 江苏大学 | A kind of method of active carbon deposit component in acquisition catalytic pyrolysis of biomass |
| CN112007687A (en) * | 2020-08-11 | 2020-12-01 | 东南大学 | Catalyst modification method for improving yield of biomass catalytic pyrolysis hydrocarbons |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040249226A1 (en) * | 2003-06-03 | 2004-12-09 | Wu An-Hsiang | Selective para-xylene production via methylation of toluene with methanol in the presence of modified HZSM-5 catalyst |
| CN101138734A (en) * | 2007-09-28 | 2008-03-12 | 东南大学 | Method for improving catalyst reacting activity in the propylene producing through propane dehydrogenation |
| CN102513143A (en) * | 2011-11-25 | 2012-06-27 | 中国石油大学(华东) | Preparation method of catalyst for catalyzing aromatization modification of gasoline |
| CN103657708A (en) * | 2012-09-07 | 2014-03-26 | 中国石油天然气集团公司 | Catalyst for aromatization and quality modification of catalytic gasoline |
| CN104357076A (en) * | 2014-11-10 | 2015-02-18 | 东南大学 | Double-stage catalytic reaction method for enhancing quality of biomass pyrolysis oil |
-
2015
- 2015-03-18 CN CN201510119924.8A patent/CN104785287A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040249226A1 (en) * | 2003-06-03 | 2004-12-09 | Wu An-Hsiang | Selective para-xylene production via methylation of toluene with methanol in the presence of modified HZSM-5 catalyst |
| CN101138734A (en) * | 2007-09-28 | 2008-03-12 | 东南大学 | Method for improving catalyst reacting activity in the propylene producing through propane dehydrogenation |
| CN102513143A (en) * | 2011-11-25 | 2012-06-27 | 中国石油大学(华东) | Preparation method of catalyst for catalyzing aromatization modification of gasoline |
| CN103657708A (en) * | 2012-09-07 | 2014-03-26 | 中国石油天然气集团公司 | Catalyst for aromatization and quality modification of catalytic gasoline |
| CN104357076A (en) * | 2014-11-10 | 2015-02-18 | 东南大学 | Double-stage catalytic reaction method for enhancing quality of biomass pyrolysis oil |
Non-Patent Citations (1)
| Title |
|---|
| HUIYAN ZHANG,ET AL.,: ""Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5"", 《BIORESOURCE TECHNOLOGY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126901A (en) * | 2015-09-14 | 2015-12-09 | 青岛大学 | Molecular sieve catalyst applied to seaweed liquefaction reaction and preparation method thereof |
| CN106732754A (en) * | 2017-01-23 | 2017-05-31 | 东南大学 | The sour dealuminzation method for preparing catalyst of hydro carbons yield is improved for biomass pyrolytic |
| CN108774538A (en) * | 2018-05-04 | 2018-11-09 | 江苏大学 | A kind of method of active carbon deposit component in acquisition catalytic pyrolysis of biomass |
| CN112007687A (en) * | 2020-08-11 | 2020-12-01 | 东南大学 | Catalyst modification method for improving yield of biomass catalytic pyrolysis hydrocarbons |
| CN112007687B (en) * | 2020-08-11 | 2021-08-03 | 东南大学 | Catalyst modification method for improving yield of biomass catalytic pyrolysis hydrocarbons |
| WO2022032959A1 (en) * | 2020-08-11 | 2022-02-17 | 东南大学 | Catalyst modification method for increasing yield of hydrocarbons by catalytic pyrolysis of biomass |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zainan et al. | Quality of bio-oil from catalytic pyrolysis of microalgae Chlorella vulgaris | |
| Zhang et al. | Microwave-assisted catalytic fast pyrolysis of biomass for bio-oil production using chemical vapor deposition modified HZSM-5 catalyst | |
| Zhang et al. | Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5 | |
| Zhang et al. | Characterization, preparation, and reaction mechanism of hemp stem based activated carbon | |
| Zhang et al. | The comparison of chemical liquid deposition and acid dealumination modified ZSM-5 for catalytic pyrolysis of pinewood using pyrolysis-gas chromatography/mass spectrometry | |
| CN106179444B (en) | A kind of preparation method of activated carbon supported carbon doped graphite phase carbon nitride | |
| Wang et al. | A comparative study on the quality of bio-oil derived from green macroalga Enteromorpha clathrata over metal modified ZSM-5 catalysts | |
| CN104785287A (en) | Modification method for improving stability of catalyst in catalytic pyrolysis of biomass | |
| Dai et al. | Enhancement of aromatics production from catalytic pyrolysis of biomass over HZSM-5 modified by chemical liquid deposition | |
| CN108499598A (en) | It is a kind of multistage porous molecular sieve N-Meso-ZSM-5 catalyst and its catalysis pyrolysis lignin prepare bio oil method | |
| Vichaphund et al. | Selective aromatic formation from catalytic fast pyrolysis of Jatropha residues using ZSM-5 prepared by microwave-assisted synthesis | |
| CN107537555B (en) | Mo/HZSM-5 catalyst, preparation method and application thereof | |
| CN103342348A (en) | Preparation method for graphene/carbon microsphere composite | |
| CN105036116B (en) | The method that kerosene co grinding method residue prepares mesophase pitch or carbonaceous mesophase spherules | |
| CN104560091B (en) | A kind of preparation method rich in light aromatics bio oil | |
| CN104557423A (en) | Method for preparing arene by directly converting methane | |
| CN108043407A (en) | A kind of Co/ sepiolites catalyst and its preparation method and application | |
| CN106492815A (en) | A kind of biomass gasification tar cracking Fe base catalyst and preparation method thereof | |
| CN108587669B (en) | A kind of shale gas oil-based drill cuttings resource utilization method | |
| CN114790397A (en) | Method for preparing electrode material by polymerizing and modifying biomass pyrolysis oil | |
| CN109675550A (en) | A kind of molybdenum-boron/sepiolite catalyst and its preparation method and application | |
| CN106554821B (en) | The method that aromatic hydrocarbons and porous charcoal/solid acid rich in dimethylbenzene are prepared from bio oil | |
| CN108906098A (en) | A kind of mesoporous TiO 2 cladding catalyst of phosphatizing nickel constitutes the preparation method of core-shell structure catalyst | |
| CN107233888A (en) | Biomass prepares gas combustion multifunction catalyst and preparation method | |
| Wu et al. | Optimizing catalytic fast pyrolysis of biomass for hydrocarbon yield |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150722 |