CN109225141A - 用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用 - Google Patents
用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用 Download PDFInfo
- Publication number
- CN109225141A CN109225141A CN201811222707.1A CN201811222707A CN109225141A CN 109225141 A CN109225141 A CN 109225141A CN 201811222707 A CN201811222707 A CN 201811222707A CN 109225141 A CN109225141 A CN 109225141A
- Authority
- CN
- China
- Prior art keywords
- carbon
- room temperature
- formaldehyde
- water absorption
- absorption rate
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
本发明涉及一种用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用,所述的碳基常温净化材料为表面官能团调控过的活性炭,所选择的官能团为羧基和氨基,采用分步等体积浸渍法制备,所选用的试剂为草酸和氨水,其中草酸溶液的质量分数为0.25%~0.50%,氨水的浓度为2.5%~5.0%。该制备方法简单、易操作、成本低。该方法可以大大提高碳基材料对于甲醛的去除率,常温下对甲醛的去除率可达到100%。
Description
技术领域
本发明属于催化环保技术领域,具体涉及一种用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用。
背景介绍
甲醛是室内空气污染物中最常见也是毒性最大的污染物之一,主要来源于家具、木制品板材和填料、织物、涂料、墙纸、地毯甚至窗帘。实测数据说明,一般正常装修的情况下,甲醛的含量可超标6倍以上,个别则有可能超标达40倍以上,室内甲醛的释放期会持续3-15年。当甲醛浓度大于 0.08m³ 就会引起喉咙不适、声音嘶哑、胸闷、气喘、皮炎等。长期、低浓度接触甲醛会引起头痛、乏力、感觉障碍、免疫力下降等症状,并且世界卫生组织确定甲醛具有致癌性,长期接触甲醛会增大患上特殊癌症的几率。在大气环境污染日益严重的今天,如何有效去除室内空气污染物中的甲醛是亟待解决的科学难题。
近年来,对甲醛污染物的控制主要分为两个方向:一个是从源头上减少甲醛污染物的产生;另一方面是采用空气净化设备。从源头上减少控制甲醛污染物主要是开发和使用更环保的材料,其中包括水性涂料、环保粘结剂、环保板材等材料的开发。但目前大部分装修装饰材料仍然存在甲醛污染问题。因此,室内空气净化设备引起了越来越多的关注,也逐步进入了广大家庭。各种空气净化产品如雨后春笋般涌现。中国作为发展中的大国,在空气治理方面具有更大的挑战,同时也具有更为广阔的市场空间。越来越严格的环境政策的出台,人们环保意识的日益增强,以及污染日趋严重的污染现状,直接激发了空气净化行业的飞速发展。据有关部门预测,目前中国室内环境净化治理产业规模达200亿元人民币。未来几年内,国内室内环境净化治理产业将处于快速成长期,预测保持每年28%的复合增长率。高性能常温甲醛净化材料的开发具有很高的现实意义。
但目前市面上绝大多数用于甲醛去除的材料多为活性炭吸附材料,众所周知,单纯的吸附材料存在多种问题:(1)针对目标污染物选择性低;(2)吸附易饱和;(3)存在二次污染。本发明所述的用于甲醛去除的多官能团碳基常温净化材料主要根据目标污染物甲醛的官能团特征,对活性炭表面进行官能团修饰,从而提高碳基材料对于甲醛去除的选择性。且本发明所述的多官能团碳基材料主要通过表面官能团与甲醛的相互作用,减少由于脱附造成的二次污染。
发明内容
为了克服现有技术的不足,在现有研究基础上进一步提高碳基材料对甲醛的选择性,减少二次污染,本发明的目的在于提供一种用于甲醛去除的多管能团碳基常温净化材料的制备方法。
本发明的再一目的在于:提供一种上述方法制备的用于甲醛去除的多官能团碳基常温净化材料产品。
本发明的又一目的在于:提供一种上述产品的应用。
本发明目的通过下述方案实现:一种用于甲醛去除的多官能团碳基常温净化材料的制备方法,其特征在于,所述的碳基常温净化材料为表面官能团调控过的活性炭,所选择的官能团为羧基和氨基,采用分步等体积浸渍法制备,包含以下步骤:
(1)活性炭基材置于100oC烘箱中活化处理3h;
(2)测量活化后的活性炭载体的吸水率;
(3)根据所测得的吸水率,采用等体积浸渍法浸渍0.25%~0.50%的草酸溶液,将浸渍好的活性炭于室温下过夜静置,然后于80oC干燥12h;
(4)测量浸渍好草酸溶液活性炭的吸水率;
(5)按测量得到的吸水率等体积浸渍2.5%~5.0%的氨水溶液,将浸渍好的活性炭于室温下过夜静置,然后于50oC小干燥12h,得到本发明所述的碳基材料。
本发明提供一种用于甲醛去除的多官能团碳基常温净化材料,根据上述所述方法制备得到。
本发明提供一种多官能团碳基常温净化材料用于甲醛去除的应用。
该制备方法简单、易操作、成本低。该方法可以大大提高碳基材料对于甲醛的去除率,常温下对甲醛的去除率可达到100%。
本发明中所述一种用于甲醛去除的多官能团碳基常温净化材料及其制备方法,相较于现有碳基材料,具有如下特点:(1)本发明所述碳基净化材料制备方法简单、价格低廉;(2)本发明所述碳基材料在制备过程中不产生废液,不会造成二次污染;(3)本发明所述用于甲醛去除的多官能团碳基净化材料相较现有活性炭吸附材料对甲醛吸附的选择性提高,去除率提高。(4)本发明主要通过甲醛与碳基材料表面官能团相互作用,结合牢固,不易造成二次污染。
具体实施方式
对比例1
称取活性炭基底材料测吸水率,根据所测得的吸水率等体积浸渍0.50%的草酸溶液,将浸渍好草酸的活性炭于室温下过夜静置,然后于80oC干燥12h,得到的碳基材料记作AC-1。
对比例2
称取活性炭基底材料测吸水率,根据所测得的吸水率等体积浸渍
5.0%的氨水溶液,将浸渍好氨水的活性炭于室温下过夜静置,然后于50oC小干燥12h,得到的碳基材料记作AC-2。
实施例1
称取100 oC活化3h的活性炭测量吸水率,根据所测得的吸水率等体积浸渍0.25%的草酸溶液,将浸渍好草酸的活性炭于室温下过夜静置,然后于80oC干燥12h,得到的草酸处理过的碳基材料。测量草酸处理过的碳基材料的吸水率,根据所测得的吸水率等体积浸渍
2.5%的氨水溶液,将浸渍好氨水的活性炭于室温下过夜静置,然后于50oC小干燥12h,得到的碳基材料记作AC-3。
实施例2
称取100 oC活化3h的活性炭测量吸水率,根据所测得的吸水率等体积浸渍0.25%的草酸溶液,将浸渍好草酸的活性炭于室温下过夜静置,然后于80oC干燥12h,得到的草酸处理过的碳基材料。测量草酸处理过的碳基材料的吸水率,根据所测得的吸水率等体积浸渍
5.0%的氨水溶液,将浸渍好氨水的活性炭于室温下过夜静置,然后于50oC小干燥12h,得到的碳基材料记作AC-4。
实施例3
称取100 oC活化3h的活性炭测量吸水率,根据所测得的吸水率等体积浸渍0.50%的草酸溶液,将浸渍好草酸的活性炭于室温下过夜静置,然后于80oC干燥12h,得到的草酸处理过的碳基材料。测量草酸处理过的碳基材料的吸水率,根据所测得的吸水率等体积浸渍
2.5%的氨水溶液,将浸渍好氨水的活性炭于室温下过夜静置,然后于50oC小干燥12h,得到的碳基材料记作AC-5。
实施例4
称取100 oC活化3h的活性炭测量吸水率,根据所测得的吸水率等体积浸渍0.50%的草酸溶液,将浸渍好草酸的活性炭于室温下过夜静置,然后于80oC干燥12h,得到的草酸处理过的碳基材料。测量草酸处理过的碳基材料的吸水率,根据所测得的吸水率等体积浸渍
5.0%的氨水溶液,将浸渍好氨水的活性炭于室温下过夜静置,然后于50oC小干燥12h,得到的碳基材料记作AC-6。
甲醛催化剂性能评价
在连续流动固定床装置中测试其性能。气体总流量为500ml/min,反应压力为常压~1atm,甲醛的初始浓度为2ppm(V/V),样品用量为0.2g。催化性能测试结果如下表1:
从表1的结果可以看出,此方法所制备的甲醛净化材料对于空气中甲醛的去除具有较好的效果,在室温下转化率能达到100%,且本发明公开的制备方法简单、成本低廉、且不产生废水,具有很高的实用价值。
Claims (3)
1.一种用于甲醛去除的多官能团碳基常温净化材料的制备方法,其特征在于,所述的碳基常温净化材料为表面官能团调控过的活性炭,所选择的官能团为羧基和氨基,采用分步等体积浸渍法制备,包含以下步骤:
(1)活性炭基材置于100oC烘箱中活化处理3h;
(2)测量活化后的活性炭载体的吸水率;
(3)根据所测得的吸水率,采用等体积浸渍法浸渍0.25%~0.50%的草酸溶液,将浸渍好的活性炭于室温下过夜静置,然后于80oC干燥12h;
(4)测量浸渍好草酸溶液活性炭的吸水率;
(5)按测量得到的吸水率等体积浸渍2.5%~5.0%的氨水溶液,将浸渍好的活性炭于室温下过夜静置,然后于50oC小干燥12h,得到本发明所述的碳基材料。
2.一种用于甲醛去除的多官能团碳基常温净化材料,其特征在于根据权利要求1所述方法制备得到。
3.一种根据权利要求2所述多官能团碳基常温净化材料用于甲醛去除的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811222707.1A CN109225141A (zh) | 2018-10-19 | 2018-10-19 | 用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811222707.1A CN109225141A (zh) | 2018-10-19 | 2018-10-19 | 用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109225141A true CN109225141A (zh) | 2019-01-18 |
Family
ID=65080854
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811222707.1A Pending CN109225141A (zh) | 2018-10-19 | 2018-10-19 | 用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109225141A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115487776A (zh) * | 2021-11-26 | 2022-12-20 | 北京科技大学 | 一种酮类VOCs吸附剂及其制备方法和应用 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2502671A4 (en) * | 2009-11-19 | 2013-05-29 | Korea Res Inst Chem Tech | CRYSTALLINE AND POROUS ORGANIC / INORGANIC HYBRID MATERIAL AND METHOD OF MANUFACTURING THEREOF |
CN104607151A (zh) * | 2015-02-13 | 2015-05-13 | 福建省鑫森炭业股份有限公司 | 一种除甲醛活性炭及制备方法 |
CN106861625A (zh) * | 2017-04-17 | 2017-06-20 | 东南大学 | 一种改性活性炭的制备方法 |
CN107282003A (zh) * | 2017-07-04 | 2017-10-24 | 北京林业大学 | 一种高效去除空气中甲醛的改性活性炭的制备方法 |
CN107583608A (zh) * | 2017-10-19 | 2018-01-16 | 上海纳米技术及应用国家工程研究中心有限公司 | 双功能材料的原位制备方法及其产品和应用 |
CN107854981A (zh) * | 2017-11-08 | 2018-03-30 | 山西新华化工有限责任公司 | 甲醛净化材料及其制备方法 |
CN107876015A (zh) * | 2017-11-16 | 2018-04-06 | 山东大学 | 一种复合活性多孔碳材料及其制备方法和应用 |
KR20180077899A (ko) * | 2016-12-29 | 2018-07-09 | 주식회사 마디 | 포름알데히드 가스 제거용 활성탄소 및 그 제조방법 |
CN108554383A (zh) * | 2018-03-26 | 2018-09-21 | 中山市洁鼎过滤制品有限公司 | 一种常温甲醛吸附剂及其制备方法和应用 |
-
2018
- 2018-10-19 CN CN201811222707.1A patent/CN109225141A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2502671A4 (en) * | 2009-11-19 | 2013-05-29 | Korea Res Inst Chem Tech | CRYSTALLINE AND POROUS ORGANIC / INORGANIC HYBRID MATERIAL AND METHOD OF MANUFACTURING THEREOF |
CN104607151A (zh) * | 2015-02-13 | 2015-05-13 | 福建省鑫森炭业股份有限公司 | 一种除甲醛活性炭及制备方法 |
KR20180077899A (ko) * | 2016-12-29 | 2018-07-09 | 주식회사 마디 | 포름알데히드 가스 제거용 활성탄소 및 그 제조방법 |
CN106861625A (zh) * | 2017-04-17 | 2017-06-20 | 东南大学 | 一种改性活性炭的制备方法 |
CN107282003A (zh) * | 2017-07-04 | 2017-10-24 | 北京林业大学 | 一种高效去除空气中甲醛的改性活性炭的制备方法 |
CN107583608A (zh) * | 2017-10-19 | 2018-01-16 | 上海纳米技术及应用国家工程研究中心有限公司 | 双功能材料的原位制备方法及其产品和应用 |
CN107854981A (zh) * | 2017-11-08 | 2018-03-30 | 山西新华化工有限责任公司 | 甲醛净化材料及其制备方法 |
CN107876015A (zh) * | 2017-11-16 | 2018-04-06 | 山东大学 | 一种复合活性多孔碳材料及其制备方法和应用 |
CN108554383A (zh) * | 2018-03-26 | 2018-09-21 | 中山市洁鼎过滤制品有限公司 | 一种常温甲醛吸附剂及其制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
S.SURESH ET AL.: ""Removal of formaldehyde on carbon-based materials: A review of the recent approaches and findings"", 《CARBON》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115487776A (zh) * | 2021-11-26 | 2022-12-20 | 北京科技大学 | 一种酮类VOCs吸附剂及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Suresh et al. | Removal of formaldehyde on carbon-based materials: A review of the recent approaches and findings | |
CN104436999B (zh) | 一种甲醛吸收剂及其使用方法 | |
Saha et al. | Batch and continuous (fixed-bed column) biosorption of crystal violet by Artocarpus heterophyllus (jackfruit) leaf powder | |
CN106861622B (zh) | 一种处理富营养化水体的水处理剂 | |
CN102350318B (zh) | 一种甲醛吸附树脂及其制备方法 | |
CN107649094A (zh) | 净化甲醛复合材料的制备方法及其产品和应用 | |
CN102627277B (zh) | 一种改性活性炭及用其去除集约化养殖场中氨气的方法 | |
CN105289593A (zh) | 一种室温条件下长效消除甲醛的载微纳米银活性炭的制备方法 | |
CN107983320A (zh) | 用于甲醛去除的双功能薄膜的制备方法及其产品和应用 | |
CN101862638B (zh) | 一种甲醛吸附剂的制备方法 | |
CN105148836A (zh) | 一种催化分解型空气净化材料及其制备方法 | |
CN109261150A (zh) | 一种低温氨选择性氧化催化剂及其制备方法、用途和使用方法 | |
CN110339810A (zh) | 一种甲醛吸附用活性炭及其制备方法 | |
CN109225141A (zh) | 用于甲醛去除的多官能团碳基常温净化材料的制备方法及产品和应用 | |
CN110237822A (zh) | 一种活性炭的环保疏水改性方法 | |
CN202866213U (zh) | 一种可有效吸附分解甲醛的纸面石膏板 | |
CN107973295B (zh) | 一种高性能除甲醛活性炭的制备方法 | |
CN106140175A (zh) | 一种催化燃烧含氟、氯VOCs催化剂的制备方法 | |
CN106076301A (zh) | 琥珀酸酐改性柚子皮吸油材料的制备方法 | |
CN108906006A (zh) | 一种可高效吸附甲醛的改性石墨烯海绵的制备方法 | |
CN101653618A (zh) | 一种甲醛去除剂及其制备方法 | |
CN107185482B (zh) | 一种用于吸附苯乙烯废气的粘土基复合吸附材料及其制备方法 | |
CN109517460A (zh) | 板材用的硅藻涂料 | |
CN110841627B (zh) | 稀土修饰的吸附富集-催化氧化双功能催化剂及其制备方法和应用 | |
CN201565231U (zh) | 气体净化活性炭包 |
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: 20190118 |
|
RJ01 | Rejection of invention patent application after publication |