CN111298774A - Preparation method of nano repair material for heavy metal polluted groundwater - Google Patents
Preparation method of nano repair material for heavy metal polluted groundwater Download PDFInfo
- Publication number
- CN111298774A CN111298774A CN201911256858.3A CN201911256858A CN111298774A CN 111298774 A CN111298774 A CN 111298774A CN 201911256858 A CN201911256858 A CN 201911256858A CN 111298774 A CN111298774 A CN 111298774A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- composite material
- carbon composite
- nano
- carboxyl carbon
- 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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a nano repair material for heavy metal polluted groundwater, which comprises the steps of mixing, drying and roasting sodium gluconate and iron salt to obtain a Fe3O 4/carboxyl carbon composite material, wherein the composite material has high-efficiency adsorption performance on heavy metals, but the adsorption capacity is low, so that the material is mixed with sodium alginate, a trace amount of graphene oxide is added, after the graphene oxide is uniformly dry-ground, chitosan is added for reaction under an acidic condition, in the process, the graphene oxide is used as a carrier, and the chitosan and the sodium alginate are adsorbed on the Fe3O 4/carboxyl carbon composite material through positive and negative charges, so that the adsorption capacity of the composite material is improved by more than 20 times, and can reach more than 3000mg/g at most.
Description
Technical Field
The invention relates to the technical field of sewage treatment materials, in particular to a preparation method of a nano repair material for heavy metal polluted underground water.
Background
The treatment of heavy metals is the focus of attention in the environmental protection industry. Heavy metals cannot be biodegraded and are easily enriched in water, so that water pollution is caused, and the human health is finally harmed. There are many methods for removing heavy metal ions in water, and conventional treatment methods include chemical precipitation, membrane filtration, ion exchange, evaporation recovery, adsorption, and electrolysis, but these methods have certain disadvantages. The chemical precipitation method has large reagent consumption and is easy to generate secondary pollution; the evaporation recovery method has too large energy consumption; the ion exchange method and the activated carbon adsorption method have good effects, but the cost is too high. The traditional adsorbent has poor adsorption effect on heavy metals.
Chinese invention patent CN107349900A discloses a heavy metal adsorbent, which comprises a compound compounded by graphene and nano magnesium oxide, has a very good adsorption effect on lead ions in water, has an adsorption capacity of more than 1000mg/g, but has a much poorer adsorption effect on other heavy metal ions such as copper, chromium and the like. Chinese invention patent CN104941585A discloses a preparation method of a heavy metal adsorbent which is rich in carboxyl and can be magnetically recovered, the heavy metal adsorbent prepared by the method can efficiently adsorb chromium ions, copper ions and nickel ions, and can be magnetically recovered after heavy metal is adsorbed, but the loading capacity is less than 200 mg/g. Therefore, it is necessary to research a method for preparing a nano repair material for heavy metal polluted groundwater, which can treat heavy metal polluted groundwater with low cost and high efficiency.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a nano repair material for heavy metal polluted underground water.
The technical scheme of the invention is as follows:
a preparation method of a nano repair material for heavy metal polluted groundwater comprises the following steps:
A. dissolving sodium gluconate and iron salt in water according to a certain proportion, uniformly mixing, and placing in an oven with the temperature of 100-;
B. b, placing the colloidal body prepared in the step A in a muffle furnace for roasting at the temperature of 250-400 ℃ for 2-3.5h, cleaning with deionized water after the reaction is finished, and drying at the temperature of 50-60 ℃ to obtain Fe3O4A/carboxycarbon composite;
C. mixing Fe3O4Mixing the carboxyl carbon composite material with sodium alginate, adding graphene oxide, grinding for 40-60min by dry grinding method, adding chitosan and sodium alginate15-20% acetic acid solution (V/V), and stirring at 600-800rpm for 20-30 min;
D. then drying at 50-60 ℃, washing with deionized water to be neutral, drying at 50-60 ℃, grinding and sieving with a 80-mesh sieve.
Preferably, the iron salt is a ferric salt or a ferrous salt.
Preferably, in the step a, the mass ratio of the sodium gluconate to the iron salt is (2-8): 1.
preferably, in step C, Fe3O4The mass ratio of the/carboxyl carbon composite material to the sodium alginate to the graphene oxide to the chitosan is (6-10): 1: (0.05-0.2): (0.5-2).
Preferably, in the step C, the addition amount of the acetic acid solution is Fe3O45-8 times of the/carboxyl carbon composite material.
The invention has the advantages that: the main raw materials of the nano repairing material for heavy metal polluted groundwater are sodium gluconate and ferric salt, and Fe is obtained after mixing, drying and roasting3O4The composite material has high-efficiency adsorption performance on heavy metals, but the adsorption capacity is low, so the material is mixed with sodium alginate, a small amount of graphene oxide is added, after the graphene oxide is uniformly dry-ground, chitosan is added to react under an acidic condition, the graphene oxide is used as a carrier in the process, and Fe is used as a carrier3O4Chitosan and sodium alginate are adsorbed on the carboxyl carbon composite material through positive and negative charges, so that the adsorption capacity of the composite material is improved by more than 20 times and can reach more than 3000mg/g at most.
Detailed Description
Example 1
A preparation method of a nano repair material for heavy metal polluted groundwater comprises the following steps:
A. dissolving sodium gluconate and ferrous sulfate in water according to a certain proportion, uniformly mixing, and placing in a 120 ℃ oven to dry water to form a colloid;
B. b, placing the colloidal body prepared in the step A into a muffle furnace to be roasted for 2.5h at 350 ℃, and carrying out reverse reactionAfter the reaction is finished, washing with deionized water, and drying at 55 ℃ to obtain Fe3O4A/carboxycarbon composite;
C. mixing Fe3O4Mixing the carboxyl carbon composite material with sodium alginate, adding graphene oxide, grinding for 55min by a dry grinding method, adding chitosan and 18% acetic acid solution (V/V), and stirring at a high speed of 750rpm for 25 min;
D. then drying at 58 ℃, washing with deionized water to be neutral, drying at 58 ℃ again, grinding and sieving with a 80-mesh sieve.
In the step A, the mass ratio of the sodium gluconate to the iron salt is 6: 1.
in the step C, Fe3O4The mass ratio of the/carboxyl carbon composite material to the sodium alginate to the graphene oxide to the chitosan is 8: 1: 0.15: 1.2.
in the step C, the addition amount of the acetic acid solution is Fe3O47 times (mass ratio) of the/carboxyl carbon composite material.
Example 2
A preparation method of a nano repair material for heavy metal polluted groundwater comprises the following steps:
A. dissolving sodium gluconate and ferric sulfate in water according to a certain proportion, uniformly mixing, and drying water in a drying oven at 150 ℃ to form a colloid;
B. b, placing the colloidal body prepared in the step A into a muffle furnace to be roasted for 3.5 hours at the temperature of 250 ℃, washing with deionized water after the reaction is finished, and drying at the temperature of 50 ℃ to obtain Fe3O4A/carboxycarbon composite;
C. mixing Fe3O4Mixing the carboxyl carbon composite material with sodium alginate, adding graphene oxide, grinding for 60min by adopting a dry grinding method, adding chitosan and 15% acetic acid solution (V/V), and stirring at a high speed of 800rpm for 20 min;
D. then drying at 60 ℃, washing with deionized water to be neutral, drying at 60 ℃ again, grinding and sieving with a 80-mesh sieve.
In the step A, the mass ratio of the sodium gluconate to the ferric salt is 2: 1.
in the step C, Fe3O4The mass ratio of the/carboxyl carbon composite material to the sodium alginate to the graphene oxide to the chitosan is 10: 1: 0.05: 2.
in the step C, the addition amount of the acetic acid solution is Fe3O45 times (mass ratio) of the/carboxyl carbon composite material.
Example 3
A preparation method of a nano repair material for heavy metal polluted groundwater comprises the following steps:
A. dissolving sodium gluconate and ferric nitrate in water according to a certain proportion, uniformly mixing, and placing in a drying oven at 100 ℃ to dry water to form a colloid;
B. b, placing the colloidal body prepared in the step A into a muffle furnace to be roasted for 2 hours at 400 ℃, washing with deionized water after the reaction is finished, and drying at 60 ℃ to obtain Fe3O4A/carboxycarbon composite;
C. mixing Fe3O4Mixing the carboxyl carbon composite material with sodium alginate, adding graphene oxide, grinding for 40min by adopting a dry grinding method, adding chitosan and 20% acetic acid solution (V/V), and stirring for 30min at a high speed of 600 rpm;
D. then drying at 50 ℃, washing with deionized water to be neutral, drying at 50 ℃ again, grinding and sieving with a 80-mesh sieve.
In the step A, the mass ratio of the sodium gluconate to the ferric salt is 8: 1.
in the step C, Fe3O4The mass ratio of the/carboxyl carbon composite material to the sodium alginate to the graphene oxide to the chitosan is 6: 1: 0.2: 0.5.
in the step C, the addition amount of the acetic acid solution is Fe3O48 times (mass ratio) of the/carboxyl carbon composite material.
Comparative example 1
The Fe obtained in step B was taken out as it was from steps C and D in example 13O4A/carboxyl carbon composite material.
Comparative example 2
The graphene oxide in example 1 was removed, and the rest of the formulation and preparation method were unchanged.
The following are test examples:
1 ton of underground water (Cu in the underground water)2+Has a concentration of 212ppm, Cr6+The concentration is 151ppm, Hg2+In a concentration of 78ppm, Ni2+Has a concentration of 114ppm, Pb2+Has a concentration of 249ppm, Cd2+Concentration of 86ppm), 1000g and 100g of the repair materials of examples 1-3 and comparative examples 1-2 were added, respectively, and stirred with a mechanical stirrer at a rotation speed of 200rmp, 24 hours later, the repair materials were separated from groundwater using a magnet, and the loading of the repair materials was tested, and the specific test data are shown in tables 1 and 2.
Table 1: and the loading capacity of the repair material is 1000 g.
| Capacity g | Cu2+ | Cr6+ | Hg2+ | Ni2+ | Pb2+ | Cd2+ |
| Example 1 | 209.4 | 149.6 | 75.5 | 112.9 | 244.2 | 83.3 |
| Example 2 | 208.6 | 149.3 | 74.8 | 111.8 | 241.8 | 81.9 |
| Example 3 | 208.4 | 150.1 | 75.2 | 112.4 | 242.6 | 82.4 |
The test data show that the repair material has good adsorption effect on various heavy metals.
Table 2: the loading of various heavy metals after 100g of the repair material is added.
| Capacity g | Cu2+ | Cr6+ | Hg2+ | Ni2+ | Pb2+ | Cd2+ |
| Example 1 | 118.4 | 60.3 | 21.2 | 33.5 | 69.5 | 32.1 |
| Comparative example 1 | 6.4 | 4.3 | 0.9 | 2.1 | 3.2 | 1.9 |
| Comparative example 2 | 42.8 | 25.9 | 7.0 | 10.4 | 24.6 | 9.7 |
Compared with the traditional adsorbing material, the prepared repairing material has the advantage that the loading capacity of heavy metals is remarkably increased.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A preparation method of a nano repair material for heavy metal polluted groundwater is characterized by comprising the following steps:
A. dissolving sodium gluconate and iron salt in water according to a certain proportion, uniformly mixing, and placing in an oven with the temperature of 100-;
B. b, placing the colloidal body prepared in the step A in a muffle furnace for roasting at the temperature of 250-400 ℃ for 2-3.5h, after the reaction is finished, cleaning with deionized water, and drying at the temperature of 50-60 ℃ to obtain the Fe3O 4/carboxyl carbon composite material;
C. mixing the Fe3O 4/carboxyl carbon composite material with sodium alginate, adding graphene oxide, grinding for 40-60min by adopting a dry grinding method, adding chitosan and 15-20% acetic acid solution (V/V), and stirring for 20-30min at a high speed of 800rpm under 600-800 rpm;
D. then drying at 50-60 ℃, washing with deionized water to be neutral, drying at 50-60 ℃, grinding and sieving with a 80-mesh sieve.
2. The method for preparing the nano remediation material of heavy metal contaminated groundwater of claim 1, wherein the iron salt is a ferric salt or a ferrous salt.
3. The method for preparing the nano repair material for heavy metal polluted groundwater according to claim 1, wherein in the step A, the mass ratio of the sodium gluconate to the iron salt is (2-8): 1.
4. the method for preparing the nano repair material for heavy metal polluted groundwater as claimed in claim 1, wherein in the step C, the mass ratio of the Fe3O 4/carboxyl carbon composite material, the sodium alginate, the graphene oxide and the chitosan is (6-10): 1: (0.05-0.2): (0.5-2).
5. The method for preparing nano repair material for heavy metal contaminated groundwater according to claim 1, wherein in the step C, the amount of the acetic acid solution added is 5-8 times of that of the Fe3O 4/carboxyl carbon composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911256858.3A CN111298774A (en) | 2019-12-10 | 2019-12-10 | Preparation method of nano repair material for heavy metal polluted groundwater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911256858.3A CN111298774A (en) | 2019-12-10 | 2019-12-10 | Preparation method of nano repair material for heavy metal polluted groundwater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111298774A true CN111298774A (en) | 2020-06-19 |
Family
ID=71144864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911256858.3A Pending CN111298774A (en) | 2019-12-10 | 2019-12-10 | Preparation method of nano repair material for heavy metal polluted groundwater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111298774A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029144A (en) * | 2009-09-29 | 2011-04-27 | 淮海工学院 | Adsorbent for adsorbing heavy metal ions and dye in waste water and preparation method thereof |
| CN103804828A (en) * | 2014-02-14 | 2014-05-21 | 江南大学 | Compound hydrogel capable of adsorbing heavy metal ions and preparation method of compound hydrogel |
| CN104941585A (en) * | 2015-05-27 | 2015-09-30 | 江苏大学 | Preparation method of carboxyl enriched and magnetically recovered heavy metal adsorbent |
| WO2019223223A1 (en) * | 2018-05-22 | 2019-11-28 | 华南理工大学 | Iron-modified chitosan/vermiculite composite material for simultaneously removing anion and cation heavy metals, and preparation and application thereof |
-
2019
- 2019-12-10 CN CN201911256858.3A patent/CN111298774A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029144A (en) * | 2009-09-29 | 2011-04-27 | 淮海工学院 | Adsorbent for adsorbing heavy metal ions and dye in waste water and preparation method thereof |
| CN103804828A (en) * | 2014-02-14 | 2014-05-21 | 江南大学 | Compound hydrogel capable of adsorbing heavy metal ions and preparation method of compound hydrogel |
| CN104941585A (en) * | 2015-05-27 | 2015-09-30 | 江苏大学 | Preparation method of carboxyl enriched and magnetically recovered heavy metal adsorbent |
| WO2019223223A1 (en) * | 2018-05-22 | 2019-11-28 | 华南理工大学 | Iron-modified chitosan/vermiculite composite material for simultaneously removing anion and cation heavy metals, and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张靖宇等: "石墨烯与天然高分子复合吸附材料的研究进展", 《印染》, vol. 45, no. 5, 1 March 2019 (2019-03-01), pages 52 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2019193926A (en) | Manufacturing method of magnetic hydrothermal charcoal, and application thereof | |
| CN111203177B (en) | Efficient treatment method of EDTA-Pb wastewater | |
| CN111589416A (en) | Lanthanum modified biochar and preparation method and application thereof | |
| Zheng et al. | Banana peel carbon that containing functional groups applied to the selective adsorption of Au (III) from waste printed circuit boards | |
| CN112108123B (en) | Modified sodium alginate composite ball, preparation method thereof and application of modified sodium alginate composite ball as heavy metal ion capturing agent | |
| CN103127899A (en) | Arsenic removal absorbent-iron and copper composite oxide and preparation method of copper composite oxide | |
| CN104190360A (en) | Oxidation-load iron modified active carbon water treatment adsorbent and preparation method thereof | |
| CN110801814A (en) | Preparation method of magnetic amino walnut shell biochar novel adsorbent | |
| CN111689568A (en) | Zero-valent bimetal material and preparation method and application thereof | |
| CN112978983A (en) | Iron-based biochar-based heavy metal complexing wastewater treatment and recycling process thereof | |
| CN114011868B (en) | Arsenic-polluted soil remediation method based on red soil-ferrous sulfate compound stabilizer | |
| CN102872830A (en) | Composite adsorption material for removing molybdenum ions from natural water and preparation method for adsorption material | |
| CN110732311A (en) | crosslinked chitosan coated MoS2Adsorbent, preparation method and application thereof | |
| CN114275868A (en) | Heavy metal targeted remover and preparation method and application thereof | |
| CN107442066B (en) | Microwave carbonized persimmon peel biological adsorbent and preparation method and application thereof | |
| CN102965312A (en) | Modification method for improving bacteria heavy metal adsorption capacity, adsorbent and application thereof | |
| CN110153157B (en) | Porous iron-based adsorption material, preparation method thereof and application thereof in heavy metal contaminated soil remediation | |
| CN111298774A (en) | Preparation method of nano repair material for heavy metal polluted groundwater | |
| CN112076723A (en) | Method for preparing heavy metal adsorbent by using Fenton sludge and application | |
| CN103721689A (en) | Magnetic meso-porous silicon, preparation method of magnetic meso-porous silicon, magnetic meso-porous silicon adsorbent, preparation method and application of magnetic meso-porous silicon adsorbent | |
| CN108126667B (en) | Flocculating agent and preparation method thereof | |
| CN114713184A (en) | Heavy metal adsorbent for removing cadmium ions in water body and preparation method and application thereof | |
| CN114192109A (en) | Graphene copper-iron oxide composite adsorbent for removing arsenic in water and preparation method thereof | |
| CN109908868B (en) | Iron-based porous adsorption material, preparation method thereof and application thereof in wastewater treatment | |
| CN112934170A (en) | Magnetic nano-ore composite material for efficiently removing thallium, and preparation method and application 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: 20200619 |
|
| RJ01 | Rejection of invention patent application after publication |