CN109012645A - Perforated tubular denitrating catalyst and preparation method thereof - Google Patents
Perforated tubular denitrating catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109012645A CN109012645A CN201810902728.1A CN201810902728A CN109012645A CN 109012645 A CN109012645 A CN 109012645A CN 201810902728 A CN201810902728 A CN 201810902728A CN 109012645 A CN109012645 A CN 109012645A
- Authority
- CN
- China
- Prior art keywords
- denitrating catalyst
- perforated tubular
- preparation
- pore
- pore creating
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000011148 porous material Substances 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000004615 ingredient Substances 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 238000007493 shaping process Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 238000007569 slipcasting Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 241000264877 Hippospongia communis Species 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of perforated tubular denitrating catalyst, and raw material is passed through to extrusion forming after mixing or the wet base of tubulose is made in slip-casting shaping process, fires after wet base is dry, obtains tubulose denitrating catalyst product；The raw material includes titanium dioxide, pore creating material and other ingredients；In sintering procedure, pore creating material forms a large amount of micron order connected holes in interiors of products.The inside of catalyst of the present invention has a large amount of micron order connected holes, these holes are airflow channel, and gas can flow through inside catalysis material, and catalysis material integrally all plays catalytic action；And air-flow is divided into countless tiny Tiny pores by micron-sized hole, and sinuate duct makes Tiny pore and the continuous making contact of catalyst material, greatly improves catalytic efficiency.
Description
Technical field
The present invention relates to a kind of perforated tubular denitrating catalysts and preparation method thereof.
Background technique
Currently used denitrating catalyst is ceramic honey comb denitrating catalyst, passes through internal catalyst material and air-flow
Contact, nitrogen oxides is catalyzed as harmless nitrogen and oxygen.But the specific surface area of existing ceramic honey comb denitrating catalyst also compares
It is relatively limited, inside there is significant component of catalysis material not contact with air-flow or insufficient contact, do not play catalytic action,
Therefore having significant component of catalysis material is invalid catalysis material, this is very unfavorable for economizing on resources.And ceramic honey comb
The clear opening of denitrating catalyst is grade size, and the nitrogen oxides in air-flow need to be diffused into catalyst surface just and can be carried out catalysis
Reaction, the rate of diffusion is slower, this greatly affected the efficiency of catalysis, causes denitrating catalyst to need to prepare length left up to 1m
It is right in addition it is longer can be only achieved catalytic effect, cause the further consumption of resource, also result in catalyst preparation process do
Dry and the firing time extension, thus increases energy consumption.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of perforated tubular denitrating catalyst and preparation method thereof, the present invention
The inside of catalyst has a large amount of micron order connected holes, these holes are airflow channel, and gas can flow through catalysis material
Inside, catalysis material integrally all play catalytic action；And air-flow is divided into countless tiny micro- gas by micron-sized hole
Stream, sinuate duct makes Tiny pore and the continuous making contact of catalyst material, greatly improves catalytic efficiency.
To achieve the above object, the present invention provides a kind of preparation method of perforated tubular denitrating catalyst, and raw material is mixed
The wet base of tubulose is made by extrusion forming or slip-casting shaping process after uniformly, is fired after wet base is dry, obtains tubulose denitration catalyst
Agent product；
The raw material includes titanium dioxide, pore creating material and other ingredients；
In sintering procedure, pore creating material forms a large amount of micron order connected holes in interiors of products.
Preferably, the mass percentage of pore creating material is 1%~40% in the raw material.
Preferably, the pore creating material is inorganic pore creating material or organic pore-forming agents.
Preferably, the inorganic pore creating material is selected from ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, Si3N4, one of inorganic carbon or
It is several.
Preferably, the organic pore-forming agents are selected from sawdust, naphthalene, starch, polyvinyl alcohol, urea, methymethacrylate, gather
One or more of vinyl chloride, polystyrene.
The present invention also provides perforated tubular denitrating catalysts obtained by above-mentioned preparation method.
Preferably, there is porous structure inside the perforated tubular denitrating catalyst.
Preferably, the porous structure inside the perforated tubular denitrating catalyst is connectivity stomata.
Advantages and advantages of the present invention are to provide a kind of perforated tubular denitrating catalyst and preparation method thereof, this
The inside of invention catalyst has a large amount of micron order connected holes, these holes are airflow channel, and gas can flow through catalysis
Material internal, catalysis material integrally all play catalytic action；And micron-sized hole air-flow is divided into it is countless tiny
Tiny pore, sinuate duct make Tiny pore and the continuous making contact of catalyst material, greatly improve catalytic efficiency.
The present invention also has many advantages, such as to reduce resource and energy consumption, cost of material be low, denitration efficiency is high.
Detailed description of the invention
Fig. 1 is the micro-structure diagram (SEM) of catalyst material of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples, further description of the specific embodiments of the present invention.Following embodiment is only
For clearly illustrating technical solution of the present invention, and not intended to limit the protection scope of the present invention.
The present invention provides a kind of preparation method of perforated tubular denitrating catalyst, and raw material is passed through after mixing and is extruded into
The wet base of tubulose is made in type or slip-casting shaping process, fires after wet base is dry, obtains tubulose denitrating catalyst product；
The raw material includes titanium dioxide, pore creating material and other ingredients；
In sintering procedure, pore creating material forms a large amount of micron order connected holes in interiors of products.
The mass percentage of pore creating material is 1%~40% in the raw material.
The pore creating material is inorganic pore creating material or organic pore-forming agents.
The inorganic pore creating material is selected from ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, Si3N4, one or more of inorganic carbon.
The organic pore-forming agents be selected from sawdust, naphthalene, starch, polyvinyl alcohol, urea, methymethacrylate, polyvinyl chloride,
One or more of polystyrene.
The present invention also provides perforated tubular denitrating catalysts obtained by above-mentioned preparation method.
There is porous structure inside the perforated tubular denitrating catalyst.
Porous structure inside the perforated tubular denitrating catalyst is connectivity stomata.
The micro-structure diagram of catalyst material of the present invention is for example as shown in Figure 1.
The more specific embodiment of the present invention is as follows:
Embodiment 1
On titanium dioxide and the formula of other ingredients, the sawdust for adding 10% is pore creating material, will be formulated all materials with kneader
Material is uniformly mixed, then is formed using extrusion forming method, and molding tubular catalyst tests its catalytic performance after firing, and is tied
Fruit is as shown in table 1.
The performance test results of 1 embodiment of table, 1 gained tubular catalyst
Embodiment 2
On titanium dioxide and the formula of other ingredients, the carbon dust for adding 13% is pore creating material, will be formulated all materials with kneader
Material is uniformly mixed, then is formed using extrusion forming method, and molding tubular catalyst tests its catalytic performance after firing, and is tied
Fruit is as shown in table 2.
The performance test results of 2 embodiment of table, 2 gained tubular catalyst
The above is only a preferred embodiment of the present invention, it is noted that those skilled in the art are come
It says, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. the preparation method of perforated tubular denitrating catalyst, which is characterized in that raw material is passed through after mixing extrusion forming or
The wet base of tubulose is made in slip-casting shaping process, fires after wet base is dry, obtains tubulose denitrating catalyst product；
The raw material includes titanium dioxide, pore creating material and other ingredients；
In sintering procedure, pore creating material forms micron order connected holes in interiors of products.
2. the preparation method of perforated tubular denitrating catalyst according to claim 1, which is characterized in that pore-creating in the raw material
The mass percentage of agent is 1%~40%.
3. the preparation method of perforated tubular denitrating catalyst according to claim 1, which is characterized in that the pore creating material is nothing
Machine pore creating material or organic pore-forming agents.
4. the preparation method of perforated tubular denitrating catalyst according to claim 3, which is characterized in that the inorganic pore creating material
Selected from ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, Si3N4, one or more of inorganic carbon.
5. the preparation method of perforated tubular denitrating catalyst according to claim 3, which is characterized in that the organic pore-forming agents
Selected from one of sawdust, naphthalene, starch, polyvinyl alcohol, urea, methymethacrylate, polyvinyl chloride, polystyrene or several
Kind.
6. perforated tubular denitrating catalyst obtained by preparation method described in any one of claims 1 to 5.
7. perforated tubular denitrating catalyst according to claim 6, which is characterized in that the perforated tubular denitrating catalyst
Inside has porous structure.
8. perforated tubular denitrating catalyst according to claim 7, which is characterized in that the perforated tubular denitrating catalyst
Internal porous structure is connectivity stomata.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810902728.1A CN109012645A (en) | 2018-08-09 | 2018-08-09 | Perforated tubular denitrating catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810902728.1A CN109012645A (en) | 2018-08-09 | 2018-08-09 | Perforated tubular denitrating catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109012645A true CN109012645A (en) | 2018-12-18 |
Family
ID=64632481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810902728.1A Pending CN109012645A (en) | 2018-08-09 | 2018-08-09 | Perforated tubular denitrating catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109012645A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474565A (en) * | 2009-01-06 | 2009-07-08 | 上海瀛正科技有限公司 | Honeycomb type SCR denitration catalyst as well as preparation method thereof and equipment |
| DE102009010158A1 (en) * | 2009-02-23 | 2010-09-02 | Süd-Chemie AG | Preparing silver cuprate, useful as catalyst, preferably an oxidation catalyst in e.g. conversion of methanol to formaldehyde, comprises reacting a silver compound and copper compound in alkaline solution in the presence of porous support |
| CN102698810A (en) * | 2012-05-14 | 2012-10-03 | 清华大学 | Honeycomb type denitration catalyst and preparation method thereof |
| CN102755887A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Preparation method of semiconductor control rectifier (SCR) denitration catalytic agent applicable to high temperature smoke condition |
| CN103769239A (en) * | 2014-01-27 | 2014-05-07 | 济南大学 | Honeycomb-type denitration catalyst with hierarchical pore structure and preparation method for honeycomb-type denitration catalyst |
| CN103877970A (en) * | 2014-03-24 | 2014-06-25 | 中安庆华河北节能环保工程技术有限公司 | Honeycombed waste gas denitrification catalyst |
| CN105618077A (en) * | 2015-07-30 | 2016-06-01 | 盐城工学院 | Preparation method for denitration ceramic cellular catalyst and catalyst prepared by preparation method |
| CN107126950A (en) * | 2017-06-09 | 2017-09-05 | 中国石油天然气股份有限公司 | Honeycomb type denitration catalyst and preparation method thereof |
| CN107983365A (en) * | 2017-12-15 | 2018-05-04 | 江苏龙净科杰催化剂再生有限公司 | Using titanium foam as VOCs catalyst of carrier and preparation method thereof |
-
2018
- 2018-08-09 CN CN201810902728.1A patent/CN109012645A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474565A (en) * | 2009-01-06 | 2009-07-08 | 上海瀛正科技有限公司 | Honeycomb type SCR denitration catalyst as well as preparation method thereof and equipment |
| DE102009010158A1 (en) * | 2009-02-23 | 2010-09-02 | Süd-Chemie AG | Preparing silver cuprate, useful as catalyst, preferably an oxidation catalyst in e.g. conversion of methanol to formaldehyde, comprises reacting a silver compound and copper compound in alkaline solution in the presence of porous support |
| CN102698810A (en) * | 2012-05-14 | 2012-10-03 | 清华大学 | Honeycomb type denitration catalyst and preparation method thereof |
| CN102755887A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Preparation method of semiconductor control rectifier (SCR) denitration catalytic agent applicable to high temperature smoke condition |
| CN103769239A (en) * | 2014-01-27 | 2014-05-07 | 济南大学 | Honeycomb-type denitration catalyst with hierarchical pore structure and preparation method for honeycomb-type denitration catalyst |
| CN103877970A (en) * | 2014-03-24 | 2014-06-25 | 中安庆华河北节能环保工程技术有限公司 | Honeycombed waste gas denitrification catalyst |
| CN105618077A (en) * | 2015-07-30 | 2016-06-01 | 盐城工学院 | Preparation method for denitration ceramic cellular catalyst and catalyst prepared by preparation method |
| CN107126950A (en) * | 2017-06-09 | 2017-09-05 | 中国石油天然气股份有限公司 | Honeycomb type denitration catalyst and preparation method thereof |
| CN107983365A (en) * | 2017-12-15 | 2018-05-04 | 江苏龙净科杰催化剂再生有限公司 | Using titanium foam as VOCs catalyst of carrier and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| PENG ZHAO ET AL.: ""Template-free synthesis of hierarchically macro-mesoporous Mn-TiO2 catalysts for selective reduction of NO with NH3"", 《FRONTIERS OF CHEMICAL SCIENCE AND ENGINEERING 》 * |
| 谷华春: ""低钒含量的V2O5-WO3/TiO2脱硝催化剂的制备及性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105008050B (en) | Ceramic honeycomb structural body and its manufacture method | |
| CN103769239B (en) | Honeycomb type denitrating catalyst with hierarchical porous structure and preparation method thereof | |
| CN109731569A (en) | Cellular SCR denitration and preparation method with three-dimensional multistage cellular structure | |
| CN105170136A (en) | High specific surface area honeycomb type denitration catalyst and preparation method thereof | |
| CN102698810B (en) | Honeycomb type denitration catalyst and preparation method thereof | |
| JP2013212500A (en) | Honeycomb structure and honeycomb catalyst body | |
| JP2014195784A (en) | Honeycomb catalytic body | |
| WO2007057496A1 (en) | Method for the preparation of metal or metal oxide catalysts that are supported on porous materials | |
| CN104445181B (en) | A kind of active carbon and preparation method thereof | |
| CN106215949A (en) | A kind of low-temperature selective catalytic reduction denitration catalyst and preparation method thereof | |
| CN109012645A (en) | Perforated tubular denitrating catalyst and preparation method thereof | |
| JPH02502445A (en) | Catalyst and its manufacturing method | |
| JP2017177075A (en) | Honeycomb catalyst, and method for producing honeycomb catalyst | |
| JPH0571547B2 (en) | ||
| CN113398919B (en) | Method for preparing coating type denitration catalyst from municipal sludge | |
| CN105964239B (en) | The preparation method of spherical denitrating catalyst | |
| CN104971780B (en) | A kind of honeycomb fashion SCR denitration and preparation method thereof | |
| CN108126692A (en) | Good automobile-used extruded type SCR denitration of a kind of low temperature active and preparation method thereof | |
| CN106582610A (en) | Vehicle-use high-mesh-number extrusive-type SCR denitration catalyst and preparation method thereof | |
| CN108927145B (en) | Preparation method of flue gas denitration catalyst | |
| CN112808265A (en) | High-strength manganese oxide particle catalyst and preparation process thereof | |
| CN204147880U (en) | Oval ceramic honeycomb carrier | |
| CN105983448B (en) | Honeycomb structure | |
| CN116265113A (en) | Integral extrusion type molecular sieve based methanol-SCR denitration catalyst and preparation method and application thereof | |
| CN112536061B (en) | Exhaust gas treatment catalyst and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181218 |
|
| RJ01 | Rejection of invention patent application after publication |