CN103432984A - Adsorbent prepared by modification of ammonia water and preparation method - Google Patents
Adsorbent prepared by modification of ammonia water and preparation method Download PDFInfo
- Publication number
- CN103432984A CN103432984A CN2013103495919A CN201310349591A CN103432984A CN 103432984 A CN103432984 A CN 103432984A CN 2013103495919 A CN2013103495919 A CN 2013103495919A CN 201310349591 A CN201310349591 A CN 201310349591A CN 103432984 A CN103432984 A CN 103432984A
- Authority
- CN
- China
- Prior art keywords
- mof
- activation
- ammonia spirit
- adsorbent
- 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
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an adsorbent prepared by modification of ammonia water and a preparation method. The preparation method comprises the following steps: (1) dipping Mg-MOF-74 in an ammonia water solution, and carrying out oscillation treatment; (2) sequentially filtering, drying, washing, filtering, drying and activating the mixture obtained in the step (1), so that the ammonia water modified adsorbent NH3@Mg-MOF-74 is obtained. The adsorbent prepared by adopting the method can not only improve the hydrophobicity of material, but also obviously improve the adsorption capacity of CO2 which is better than the adsorption capacity of the raw material Mg-MOF-74 under the condition of low CO2 concentration.
Description
Technical field
The present invention relates to prepare a kind of novel absorption material that CO2 is there is high-adsorption-capacity under the low pressure condition, relate in particular to a kind of adsorbent NH that adopts the ammoniacal liquor modification to prepare
3@Mg-MOF-74 and preparation method.
Background technology
People on average have the time more than 80% to spend indoor about every day according to investigations.Therefore, the quality of room air and the relation of health just seem closer, also just more important to the health of human body.The World Health Organization confirms: the mankind 68% disease is relevant with room air pollution, and room air pollution is more serious more than 5 times than outdoor air pollution.CO2 is one of main component of room air pollution, and the number of CO2 content can reflect the level of aggregation of indoor environment.The content of indoor CO2 is generally all higher than outdoor, indoor CO2 mainly from people the breathe out gas that produces and the burning (gas-cooker, coal stove for heating etc.) of some fuel.
CO2 is the essential material of Human Physiology, belongs to the respiratory center excitatory substance, so the CO2 of low concentration can not produce too much influence to the healthy of people.But when its concentration surpasses certain limit (> 1000ppm) can produce toxic action to people's health.High concentration CO 2 can cause central nervous system poisoning, make respiratory center continue excited after sensitivity reduce, finally cause paralysis and suffocate, make the body anoxic and produce many irreversible lesion as shown in table 1-1.
The main impression of human body under CO2 concentration in table 1-1 different chamber
China is to indoor CO
2being defined as of concentration is less than 1000ppm.Therefore, the indoor CO of development of new
2concentration is controlled material and is necessary.
For the environment of south China humidity, the adsorbent of developing a kind of low concentration CO 2 must possess certain hydrophobicity performance.Under low humidity (RH=10%), the Mg-MOF-74 water absorbing properties is more intense, and this must be to its CO
2absorption property has adverse influence.So, how to study modification Mg-MOF-74 material, its hydrophobicity performance is descended and be even more important.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide the modification of a kind of employing ammoniacal liquor to prepare new adsorbent NH
3the method of@Mg-MOF-74, with the hydrophobicity performance of lower cost improvement material, improve it is under the 1000ppm condition in gas concentration simultaneously, for the absorption property of CO2.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method that adopts the ammoniacal liquor modification to prepare adsorbent, comprise the steps:
(1) by the Mg-MOF-74 material soaking in ammonia spirit, and carry out oscillation treatment;
(2) step (1) gained mixture is filtered successively, dry, rinse, filter, dry, activation, obtain the adsorbent NH after the ammoniacal liquor modification
3@Mg-MOF-74.
The molar concentration of described ammonia spirit is 1～9mol/l.
The mass ratio of described Mg-MOF-74 and ammonia spirit is: 1:100～1:500.
The time of described oscillation treatment is 2～24h.
In step (2), the temperature of twice drying is 100～150 ℃, and the reagent that rinses use is methyl alcohol, and the temperature of activation is 150～250 ℃.
The molar concentration of described ammonia spirit is 3mol/l, and the mass ratio of Mg-MOF-74 and ammonia spirit is 1:400, and the oscillation treatment time is 24h; Twice baking temperature is 150 ℃, and activation temperature is 230 ℃.
In step (2), second filtration used the G3 sand core funnel to filter wherein residual methyl alcohol.
The preparation method of described Mg-MOF-74 is as follows:
A, magnesium nitrate hexahydrate, 2,5 dihydric para-phthalic acids are added in retort, then add wherein DMF, deionized water and ethanol; Then, put into magnetic stir bar and stir 1h on magnetic stirring apparatus, then retort is placed in to stainless steel outer sleeve and by its sealing, put into electrothermostat and carry out the temperature programming reaction, the setting heating schedule is: 10min rises to 125 ℃ from room temperature, and maintain 24h, afterwards retort is placed in to the indoor room temperature that is cooled to;
B, cooled mixture is filtered, obtain yellow solid, and rinse, filter with DMF, add DMF in the yellow solid obtained, in closed reactor and be positioned over electrothermostat, setting heating schedule: 10min is warming up to 85 ℃ and maintains 16h, then take out and be placed in indoor coolingly, then filter drying, activation, obtain flaxen Mg-MOF-74.
Described magnesium nitrate hexahydrate and 2,5 dihydric para-phthalic acids' mass ratio is 3.5～4.5; The volume ratio of DMF, deionized water and ethanol is=15:1:1.
In described step b, drying is in the vacuum drying chamber of 100 ℃, and activation is at 250 ℃ of activation 5h.
Compared with prior art, there is following beneficial effect:
(1) NH that prepared by the present invention
3@Mg-MOF-74 adsorbent is due to NH
3introducing, strengthened the alkalescence of material surface, not only can reduce the absorption property of material to water, and can strengthen again the ability of its CO absorption 2.
(2) method of the present invention, process operation is simple, easily realizes, and reproducible, ammoniacal liquor can be bought from market, and raw material is easy to get.
The accompanying drawing explanation
The NH that the ammoniacal liquor modification of Fig. 1 variable concentrations makes
3the XRD spectra of@Mg-MOF-74 material.
NH after the modification of Fig. 2 ammoniacal liquor
32 performance tests of@Mg-MOF-74 material CO absorption (CO2:1000ppm, its dividing potential drop: 0.001P
0, P wherein
0=760mmHg).
NH after the modification of Fig. 3 ammoniacal liquor
3the test of@Mg-MOF-74 material adsorbed water steam performance.
NH after the modification of Fig. 4 ammoniacal liquor
3the reperformance test of@Mg-MOF-74 material absorbing carbon dioxide.
The specific embodiment
Below in conjunction with drawings and Examples, the invention will be further described, and the present invention is not limited to this.
Embodiment 1
At first, take magnesium nitrate hexahydrate 0.6550g, 2,5 dihydric para-phthalic acid 0.1650g, and put into the polytetrafluoroethylene (PTFE) bottle, then add the N-N dimethyl formamide wherein, deionized water, alcohol mixed solution (DMF:H in mixed solution wherein
2o:CH
3cH
2the ratio of OH is=15:1:1 that actual consumption is: DMF:61.5ml, H
2o:4.1ml, CH
3cH
2oH:4.1ml); Then, then put into magnetic stir bar and stir 1h on magnetic stirring apparatus, then retort be placed in to stainless steel outer sleeve and, by its sealing, put into electrothermostat and carry out the temperature programming reaction.The setting heating schedule is: 10min rises to 125 ℃ from room temperature, and maintains 24h, afterwards retort is placed in to the indoor room temperature that is cooled to.Its mixture is filtered, obtain yellow solid, and, with after the DMF flushing, filtering several times, the yellow solid obtained is placed in to the tetrafluoroethene bottle, add a certain amount of DMF, in closed reactor and place electrothermostat, set heating schedule: 10min and be warming up to 85 ℃ and maintain 16h, then take out and be placed in indoor coolingly, then filter, dry in the vacuum drying chamber of 100 ℃, obtain flaxen Mg-MOF-74 powder at 250 ℃ of activation 5h.
Mg-MOF-74 powder 0.2 gram is joined in the ammonia spirit that molar concentration is 1mol/l (mass ratio of Mg-MOF-74 and ammonia spirit is: 1:500), the facilitating impregnation that vibrated under room temperature (25 ℃), the time is 24h.The gained mixture is filtered, 150 ℃ of dryings, by washed with methanol, use that the G3 sand core funnel filters, 150 ℃ of dryings, 150 ℃ of activation, obtain NH
3@Mg-MOF-74 adsorbent, be designated as: NH
3@Mg-MOF-74-1#.
Embodiment 2
Mg-MOF-74 powder 0.2 gram is joined in the ammonia spirit that molar concentration is 3mol/l (mass ratio of Mg-MOF-74 and ammonia spirit is: 1:400), the facilitating impregnation that vibrated under room temperature (25 ℃), the time is 24.The gained mixture is filtered, 150 ℃ of dryings, by washed with methanol, use that the G3 sand core funnel filters, 100 ℃ of dryings, 230 ℃ of activation, obtain NH
3@Mg-MOF-74 adsorbent, be designated as: NH
3@Mg-MOF-74-2#.
Embodiment 3
Mg-MOF-74 powder 0.2 gram is joined in the ammonia spirit that molar concentration is 5mol/l (mass ratio of Mg-MOF-74 and ammonia spirit is: 1:250), the facilitating impregnation that vibrated under room temperature (25 ℃), the time is 24h.The gained mixture is filtered, 150 ℃ of dryings, by washed with methanol, use that the G3 sand core funnel filters, 150 ℃ of dryings, 250 ℃ of activation, obtain NH
3@Mg-MOF-74 adsorbent, be designated as: NH
3@Mg-MOF-74-3#.
Embodiment 4
Mg-MOF-74 powder 0.2 gram is joined in the ammonia spirit that molar concentration is 7mol/l (mass ratio of Mg-MOF-74 and ammonia spirit is: 1:100), the facilitating impregnation that vibrated under room temperature (25 ℃), the time is 24h.The gained mixture is filtered, 100 ℃ of dryings, by washed with methanol, use that the G3 sand core funnel filters, 100 ℃ of dryings, 200 ℃ of activation, obtain NH
3@Mg-MOF-74 adsorbent, be designated as: NH
3@Mg-MOF-74-4#.
The material modified NH of ammoniacal liquor prepared for further illustrating various embodiments of the present invention
3@Mg-MOF-74 is good than original material Mg-MOF-74 material at performance, the hydrophobicity performance of CO absorption 2, NH prepared by the present invention
3@Mg-MOF-74 and original material Mg-MOF-74 material compare.Evaluation results is as follows:
(1) the adsorbent absorption property is estimated
The material modified NH of ammoniacal liquor prepared for each embodiment by Fig. 1
3the PXRD spectrogram of@Mg-MOF-74 can find out at 7.5 ° and locate all to occur and the consistent characteristic peak of diffraction spectrogram characteristic peak of MOF-74 with 12 ° that this shows, the NH that the modification of application ammoniacal liquor dipping obtains
3@Mg-MOF-74, have good crystal structure.
Fig. 2 shows the adsorption isotherm (at 273.15K, in 0～1atm pressure limit) on NH3@Mg-MOF-74 material prepared at each embodiment by CO2.As can be seen from the figure, (<1000ppm scope, i.e. P/P in low pressure range
0<0.001) its adsorption capacity to CO2 of NH3@Mg-MOF-74 material that, prepared by each embodiment is all apparently higher than the adsorption capacity of original Mg-MOF-74 material.NH wherein
3the adsorbance of@Mg-MOF-74-2# is the highest.
Fig. 3 shows the adsorption isotherm on NH3@Mg-MOF-74 material prepared at each embodiment by steam.As can be seen from the figure, its adsorption capacity to steam of NH3@Mg-MOF-74 material that prepared by each embodiment all is starkly lower than the adsorption capacity of original Mg-MOF-74 material.This shows serial NH prepared by the present invention
3its hydrophobicity of@Mg-MOF-74 material all obviously improves.
Fig. 4 is that the NH3@Mg-MOF-74 material after the ammoniacal liquor modification is under low pressure investigated the repeatability of carbon dioxide adsorption, as can be seen from the figure come through after the sorption cycle of three times, each material all remains unchanged substantially to the CO2 adsorbance, shows that its performance is more stable.Wherein the NH3@Mg-MOF-74-2 of embodiment 2 preparations is the highest to the adsorbance of CO2, reaches 0.66mmol/g, and the adsorbance of comparing original material improves 65%.
(2) adsorbent specific area measuring
Table 1 has been listed NH prepared by each embodiment
3the specific surface area analysis result of@Mg-MOF-74 material.Can find out the NH that the modification of application ammoniacal liquor dipping obtains
3@Mg-MOF-74, its specific area all reduces, but still has good loose structure.Although their specific area reduces to some extent, because surface alkalinty strengthens, their absorption properties to acidic molecular CO2 have but been strengthened.
NH prepared by each embodiment of table 1
3the specific area of@Mg-MOF-74 material
| Material | SBet（m 2.g -）） |
| NH3@Mg-MOF-74-1# | 720 |
| NH3@Mg-MOF-74-2# | 699 |
| NH3@Mg-MOF-74-3# | 528 |
| NH3@Mg-MOF-74-4# | 416 |
| Mg-MOF-74 | 1056 |
Claims (10)
1. a method that adopts the ammoniacal liquor modification to prepare adsorbent, is characterized in that, comprises the steps:
(1) by the Mg-MOF-74 material soaking in ammonia spirit, and carry out oscillation treatment;
(2) step (1) gained mixture is filtered successively, dry, rinse, filter, dry, activation, obtain the adsorbent after the ammoniacal liquor modification.
2. method according to claim 1, is characterized in that, the molar concentration of described ammonia spirit is 1～9mol/l; The mass ratio of described Mg-MOF-74 and ammonia spirit is: 1:100～1:500.
3. method according to claim 2, is characterized in that, the time of the described oscillation treatment of step (1) is 2～24h.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that, in step (2), the temperature of twice drying is 100～150 ℃, and the reagent that rinses use is methyl alcohol, and the temperature of activation is 150～250 ℃.
5. according to claim 1 or 2 or 3 described methods, it is characterized in that, the molar concentration of described ammonia spirit is 3mol/l, and the mass ratio of Mg-MOF-74 and ammonia spirit is 1:400, and the oscillation treatment time is 24h; Twice baking temperature is 150 ℃, and activation temperature is 230 ℃.
6. according to claim 1 or 2 or 3 described methods, it is characterized in that, in step (2), second is filtered the filtration of use G3 sand core funnel.
7. according to claim 1 or 2 or 3 described methods, it is characterized in that, the preparation method of described Mg-MOF-74 is as follows:
A, magnesium nitrate hexahydrate, 2,5 dihydric para-phthalic acids are added in retort, then add wherein DMF, deionized water and ethanol; Then, put into magnetic stir bar and stir 1h on magnetic stirring apparatus, then retort is placed in to stainless steel outer sleeve and by its sealing, put into electrothermostat and carry out the temperature programming reaction, the setting heating schedule is: 10min rises to 125 ℃ from room temperature, and maintain 24h, afterwards retort is placed in to the indoor room temperature that is cooled to;
B, cooled mixture is filtered, obtain yellow solid, and rinse, filter with DMF, add DMF in the yellow solid obtained, in closed reactor and be positioned over electrothermostat, set heating schedule: be warming up to 85 ℃ and maintain 16h, then take out and be placed in indoor coolingly, then filter drying, activation, obtain flaxen Mg-MOF-74.
8. method according to claim 7, is characterized in that, described magnesium nitrate hexahydrate and 2,5 dihydric para-phthalic acids' mass ratio is 3.5～4.5; The volume ratio of DMF, deionized water and ethanol is=15:1:1.
9. method according to claim 7, is characterized in that, in described step b, drying is in the vacuum drying chamber of 100 ℃, and activation is at 250 ℃ of activation 5h.
10. the adsorbent that prepared by claim 1～9 any one method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103495919A CN103432984A (en) | 2013-08-12 | 2013-08-12 | Adsorbent prepared by modification of ammonia water and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103495919A CN103432984A (en) | 2013-08-12 | 2013-08-12 | Adsorbent prepared by modification of ammonia water and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103432984A true CN103432984A (en) | 2013-12-11 |
Family
ID=49686753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103495919A Pending CN103432984A (en) | 2013-08-12 | 2013-08-12 | Adsorbent prepared by modification of ammonia water and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103432984A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992339A (en) * | 2014-05-21 | 2014-08-20 | 哈尔滨工业大学 | Method for synthesizing metal organic framework material Mg-MOF-74 |
| CN104001476B (en) * | 2014-05-07 | 2016-05-04 | 华南理工大学 | A kind of ammonia modified absorbing material and preparation method thereof and application |
| CN106475058A (en) * | 2016-09-30 | 2017-03-08 | 昆明理工大学 | A kind of preparation method of double-core adsorbent and method of modifying and application |
| CN106492754A (en) * | 2016-09-30 | 2017-03-15 | 昆明理工大学 | A kind of preparation method of adsorbent, method of modifying and application |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN108424008A (en) * | 2018-04-28 | 2018-08-21 | 揭阳市东信智能门窗科技有限公司 | A kind of sound insulation hollow glass and preparation method thereof |
| CN111495328A (en) * | 2020-04-24 | 2020-08-07 | 太原理工大学 | Ammonia modification method of calcium squarate and application of ammonia modification method in efficient separation of ethylene and ethane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218298A (en) * | 2011-04-28 | 2011-10-19 | 华南理工大学 | Preparation method of modified ZIF-8 zeolitic imidazolate framework material |
| CN103120931A (en) * | 2013-01-31 | 2013-05-29 | 中山大学 | Cage type carbon dioxide adsorption material as well as preparation method and application thereof |
-
2013
- 2013-08-12 CN CN2013103495919A patent/CN103432984A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218298A (en) * | 2011-04-28 | 2011-10-19 | 华南理工大学 | Preparation method of modified ZIF-8 zeolitic imidazolate framework material |
| CN103120931A (en) * | 2013-01-31 | 2013-05-29 | 中山大学 | Cage type carbon dioxide adsorption material as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| STEPHEN R.CASKEY,ET AL: "Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| ZHIJUAN ZHANG,ET AL: "Improvement of CO2 adsorption on ZIF-8 crystals modified by enhancing basicity of surface", 《CHEMICAL ENGINEERING SCIENCE》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104001476B (en) * | 2014-05-07 | 2016-05-04 | 华南理工大学 | A kind of ammonia modified absorbing material and preparation method thereof and application |
| CN103992339A (en) * | 2014-05-21 | 2014-08-20 | 哈尔滨工业大学 | Method for synthesizing metal organic framework material Mg-MOF-74 |
| CN106475058A (en) * | 2016-09-30 | 2017-03-08 | 昆明理工大学 | A kind of preparation method of double-core adsorbent and method of modifying and application |
| CN106492754A (en) * | 2016-09-30 | 2017-03-15 | 昆明理工大学 | A kind of preparation method of adsorbent, method of modifying and application |
| CN107175125A (en) * | 2017-05-31 | 2017-09-19 | 中山大学 | A kind of activation method of MOFs bases oxygen reduction electro-catalyst |
| CN108424008A (en) * | 2018-04-28 | 2018-08-21 | 揭阳市东信智能门窗科技有限公司 | A kind of sound insulation hollow glass and preparation method thereof |
| CN108424008B (en) * | 2018-04-28 | 2020-12-29 | 揭阳市东信智能门窗科技有限公司 | Sound-insulation hollow glass and preparation method thereof |
| CN111495328A (en) * | 2020-04-24 | 2020-08-07 | 太原理工大学 | Ammonia modification method of calcium squarate and application of ammonia modification method in efficient separation of ethylene and ethane |
| CN111495328B (en) * | 2020-04-24 | 2022-05-17 | 太原理工大学 | Ammonia modification method of calcium squarate and application of ammonia modification method in efficient separation of ethylene and ethane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103432984A (en) | Adsorbent prepared by modification of ammonia water and preparation method | |
| CN105056895B (en) | A kind of preparation method and applications of metal organic framework mesopore silicon oxide composite | |
| CN104495837B (en) | Sargassum-based activated carbon and preparation method and application thereof | |
| CN107362807B (en) | Mn/Co-based low-temperature SCO catalyst and preparation method thereof | |
| CN105233802B (en) | One kind doping arginic copper base metal organic framework materials of L and preparation method thereof | |
| Mumtaz et al. | Biomass waste utilization for adsorbent preparation in CO2 capture and sustainable environment applications | |
| CN108295816A (en) | A kind of normal-temperature efficient is except modified formaldehyde charcoal and preparation method thereof | |
| CN107008323B (en) | A kind of activated-carbon catalyst preparation method for flue gas desulfurization and denitrification | |
| CN105597516B (en) | Magnetic iron oxide desulfurizer and preparation method thereof | |
| CN108927170A (en) | A kind of preparation method and application of the low-temperature denitration of flue gas catalyst based on CoMnAl houghite | |
| CN104324763A (en) | Denitration and demercuration composite catalyst and preparation method thereof | |
| CN111701566A (en) | Adsorbent and preparation method and application thereof | |
| CN108479721A (en) | A kind of methyl aldehyde adsorption material and its application | |
| CN104525133A (en) | Metal-organic framework material for adsorbing N2O and preparation method thereof | |
| CN105524083B (en) | A kind of preparation of metal-organic framework material for purified natural gas | |
| CN108993530A (en) | A kind of preparation method and application of hydrotalcite NiMnTi catalyst | |
| CN108499516A (en) | Support type arsenic adsorbent and its preparation method and application and the method for arsenic removing | |
| CN103962096A (en) | Preparation method of absorbent for removing indoor low-concentration hydrogen sulfide | |
| CN109317107A (en) | A kind of opoka composite formaldehyde scavenging material and preparation method thereof | |
| CN110961077A (en) | Preparation method of titanium dioxide activated carbon composite adsorbent for cigarette filter | |
| CN110371973A (en) | A kind of poly- p-phenylenediamine/graphene-based nitrogen-doped porous carbon material preparation method | |
| CN116284063A (en) | Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof | |
| CN111004398B (en) | Microporous Cu-MOF material and preparation method and application thereof | |
| CN112387247B (en) | Modified fly ash adsorbent and preparation method thereof, and trimethylamine adsorption method | |
| CN104772117B (en) | A kind of activated carbon composite modifying method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20131211 |