CN113385125A - Preparation device and process of graphene oxide composite superfine silver powder - Google Patents
Preparation device and process of graphene oxide composite superfine silver powder Download PDFInfo
- Publication number
- CN113385125A CN113385125A CN202110266091.3A CN202110266091A CN113385125A CN 113385125 A CN113385125 A CN 113385125A CN 202110266091 A CN202110266091 A CN 202110266091A CN 113385125 A CN113385125 A CN 113385125A
- Authority
- CN
- China
- Prior art keywords
- washing
- kettle body
- reaction
- outlet
- reaction kettle
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 6
- 230000008569 process Effects 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 117
- 238000005406 washing Methods 0.000 claims abstract description 95
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 60
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 44
- 238000000967 suction filtration Methods 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 32
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 30
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 22
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 22
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000011229 interlayer Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 235000010489 acacia gum Nutrition 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 229920000084 Gum arabic Polymers 0.000 claims description 6
- 241000978776 Senegalia senegal Species 0.000 claims description 6
- 239000000205 acacia gum Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 11
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- -1 silver powder compound Chemical class 0.000 description 12
- 239000007921 spray Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000008676 import Effects 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Images
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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
- B01D29/01—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with flat filtering elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
- B01D29/76—Handling the filter cake in the filter for purposes other than for regenerating
- B01D29/86—Retarding cake deposition on the filter during the filtration period, e.g. using stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
- B01D29/96—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor in which the filtering elements are moved between filtering operations; Particular measures for removing or replacing the filtering elements; Transport systems for filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
- B01D35/16—Cleaning-out devices, e.g. for removing the cake from the filter casing or for evacuating the last remnants of liquid
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B13/00—Accessories or details of general applicability for machines or apparatus for cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/08—Cleaning containers, e.g. tanks
- B08B9/093—Cleaning containers, e.g. tanks by the force of jets or sprays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2201/00—Details relating to filtering apparatus
- B01D2201/20—Pressure-related systems for filters
- B01D2201/204—Systems for applying vacuum to filters
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a device and a process for preparing graphene oxide composite superfine silver powder, wherein the device comprises a reaction kettle assembly, a suction filtration washing assembly and a drying assembly, the reaction kettle assembly comprises a reaction kettle body, a first stirring piece extending into the reaction kettle body is further arranged on the reaction kettle body, a silver nitrate feeding port and an ascorbic acid feeding port are further arranged at the upper part of the reaction kettle body, and a reaction outlet connected with the suction filtration washing assembly is further arranged at the lower part of the reaction kettle body. Compared with the prior art, the invention can effectively solve the problems of uneven particle size, energy waste, incomplete cleaning, energy waste, large amount of human resources, low production efficiency and the like in the prior art.
Description
Technical Field
The invention belongs to the technical field of silver powder preparation devices, and relates to a preparation device and a preparation process of graphene oxide composite superfine silver powder.
Background
The key technology for producing the superfine silver powder is to control the particle size, particle size distribution and morphology during batch production, wherein the device with the largest influence is a reaction kettle. For example, patent No. CN203292491U discloses a device for preparing ultrafine silver powder by liquid phase reduction, which is used for preparing silver powders with different particle sizes and morphologies by adjusting the pH value of the reaction solution, the addition rate of the reducing agent, the stirring rate and the reaction temperature. Various parameters are easy to accurately adjust, and the method is suitable for producing small-batch and multi-variety silver powder. The disadvantages are that no liquid inlet is provided, the liquid inlet speed can not be adjusted, and the reaction temperature and the reaction state can not be monitored in real time. Patent No. CN205914165U has designed a double glazing reation kettle of preparation silver powder, and reation kettle double glazing's alkylation processing can prevent that side reaction from taking place, has improved silver powder production efficiency. However, the U-shaped jacket does not adopt a heat preservation measure, the heat loss is obvious, the energy conservation is not facilitated, the entering of the reaction liquid is too concentrated, the effective control cannot be realized, and the preparation of the silver powder is influenced. Patent No. CN203751337U discloses an apparatus for preparing silver powder by chemical deposition, in which a metal salt solution and a reducing agent solution are pressed into a spray plate and atomized and sprayed to fully react. The device has the advantages of simple structure, less investment and low processing cost, and the obtained product has uniform particle size and controllable reaction process. However, the reaction kettle adopted in the reaction is designed by stainless steel, and silver mirror reaction is easy to generate when the silver powder is prepared.
Disclosure of Invention
The invention aims to provide a device and a process for preparing graphene oxide composite superfine silver powder.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation device of graphene oxide composite superfine silver powder, which comprises a reaction kettle assembly, a suction filtration washing assembly and a drying assembly, wherein the reaction kettle assembly comprises a reaction kettle body internally provided with an interlayer, a first stirring piece extending into the reaction kettle body is further arranged on the reaction kettle body, a silver nitrate feeding port and an ascorbic acid feeding port are further arranged at the upper part of the reaction kettle body, and a reaction outlet connected with the suction filtration washing assembly is further arranged at the lower part of the reaction kettle body.
Furthermore, the reaction kettle body is also provided with a high-pressure water spray nozzle connected with external water supply equipment.
Furthermore, the side wall of the reaction kettle body is provided with an interlayer, and the interlayer is also provided with a hot water inlet and a hot water outlet which are connected with an external hot water circulation pipeline.
Furthermore, a thermometer extending into the reaction kettle body is also arranged on the reaction kettle body.
Further, the suction filtration washing assembly comprises a closed washing kettle body, a suction filtration liquid inlet is further formed in the top of the washing kettle body, a filtrate outlet is further formed in the bottom of the washing kettle body, a filter plate is further arranged in the washing kettle body, and a high-pressure spray head is further arranged on the upper portion of the washing kettle body.
Furthermore, the filtrate outlet of the washing kettle body is also connected with a vacuum box, the top of the vacuum box is also provided with a vacuum pipeline port connected with external vacuum equipment, the bottom of the vacuum box is also provided with a washing liquid outlet which can be opened and closed, and the washing liquid outlet is also connected with a waste liquid pool.
Furthermore, the filter plate comprises a filter frame and a filter element which is arranged on the filter frame and can move along the surface of the filter element in a lateral direction, a passage door is arranged on the side part of the washing kettle body, and when the passage door is opened, a suction filtration discharge port capable of taking out the filter element is formed.
Further, the drying component including import storehouse, cylinder and the export storehouse that communicates in proper order, the both ends of cylinder respectively with import storehouse and export storehouse rotate sealing connection, still are equipped with at the surface of cylinder and add the heat-insulating material, the top in import storehouse still be equipped with and be but hopper-shaped open closed dry feed inlet, the bottom in export storehouse still is equipped with open closed dry discharge gate.
Furthermore, the inlet bin is also provided with a vacuum machine.
Furthermore, the ports of the roller, which are respectively communicated with the inlet bin and the outlet bin, are also provided with openable baffles.
The second technical scheme of the invention provides a preparation process of graphene oxide composite superfine silver powder, which is implemented by adopting the device, and the preparation process comprises the following steps:
(1) dissolving gum arabic and ascorbic acid in deionized water at 50 ℃ to prepare a reducing solution, and then feeding the reducing solution into a reaction kettle body from an ascorbic acid feed inlet;
(2) then, atomizing and spraying the prepared silver nitrate solution from a silver nitrate feed inlet into the reaction kettle body;
(3) opening a first stirring piece and a hot water circulation pipeline in the reaction kettle body, reacting, conveying the obtained product into a suction filtration washing component from a reaction outlet, and washing off redundant gum arabic and unreacted ions by using water as a detergent;
(4) after the leaching and washing are finished, taking out the obtained silver powder, adding water to prepare a silver powder suspension, sending the silver powder suspension into a reaction kettle body of another reaction kettle component through an ascorbic acid feed port, simultaneously adding the prepared GO solution into the reaction kettle body, and continuously stirring and heating for reaction;
(5) and (5) conveying the reaction product obtained in the step (4) into a suction filtration washing assembly, washing by using water and absolute ethyl alcohol, and conveying the obtained solid into a drying assembly for drying to obtain the target product.
Compared with the prior art, the graphene oxide composite superfine silver powder preparation device capable of being automated and saving energy is designed by optimizing the existing equipment. The designed reaction kettle with the heatable components saves time for dissolving solute and reduces cost; the reaction kettle can monitor the reaction condition in real time, flexibly adjust according to different reaction systems, and enter the next process without blockage; in addition, the suction filtration washing assembly and the drying assembly can realize quick and thorough cleaning and quick and uniform drying of the graphene oxide composite superfine silver powder under the condition of not changing the characteristics of the silver powder.
Drawings
FIG. 1 is a schematic structural view of a reactor assembly of the present invention;
FIG. 2 is a schematic structural view of a suction filtration washing assembly of the present invention;
FIG. 3 is a schematic diagram of the construction of the drying assembly of the present invention;
FIG. 4 is a SEM and particle size distribution diagram of the composite ultrafine silver powder prepared by using the apparatus of the present invention;
FIG. 5 is a FESEM photograph of composite ultrafine silver powder prepared using the apparatus of the present invention;
the notation in the figure is:
1-a reaction kettle component, 101-a reaction kettle body, 102-an interlayer, 103-a first stirring piece, 104-a silver nitrate feeding port, 105-an ascorbic acid feeding port, 106-a reaction outlet, 107-a high-pressure water spraying port, 108-a hot water inlet, 109-a hot water outlet and 110-a thermometer;
2-a suction filtration washing component, 201-a washing kettle body, 202-a filter plate, 203-a vacuum pipeline port, 204-a washing liquid outlet, 205-a filter element, 206-a passage door, 207-a suction filtration liquid inlet, 208-a second stirring part, 209-a waste liquid pool and 210-a high-pressure spray head;
3-drying component, 31-vacuum machine, 32-inlet bin, 33-roller, 34-heating element and 35-outlet bin.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following embodiments or examples, functional components or structures that are not specifically described are all conventional components or structures in the art for achieving the corresponding functions. For example, the heating element may be any element in the art that can perform a controllable heating function, and the like.
One of the technical solutions of the present invention provides a preparation apparatus for graphene oxide composite ultrafine silver powder, the structure of which is shown in fig. 1 to fig. 3, and the apparatus comprises a reaction kettle assembly 1, a suction filtration washing assembly 2 and a drying assembly 3, wherein the reaction kettle assembly 1 comprises a reaction kettle body 101 with an interlayer 102 arranged therein, the reaction kettle body 101 is further provided with a first stirring member 103 extending into the reaction kettle body 101, the upper portion of the reaction kettle body 101 is further provided with a silver nitrate feed port 104 and an ascorbic acid feed port 105, and the lower portion of the reaction kettle body 101 is further provided with a reaction outlet 106 connected with the suction filtration washing assembly 2. Preferably, a rotary spray head is further arranged at the silver nitrate feeding hole 104.
In some embodiments, referring to fig. 1 again, the reaction vessel body 101 is further provided with a high pressure water jet 107 connected to an external water supply device.
In some embodiments, referring to fig. 1 again, the side wall of the reaction kettle body 101 is provided with an interlayer 102, and the interlayer 102 is further provided with a hot water inlet 108 and a hot water outlet 109 connected to an external hot water circulation pipeline.
In some embodiments, referring to fig. 1 again, a thermometer 110 is further disposed on the reaction vessel 101.
In some embodiments, referring to fig. 2 again, the suction filtration washing assembly 2 includes a closed washing kettle body 201, a suction filtration liquid inlet 207 is further disposed at the top of the washing kettle body 201, a filtrate outlet is further disposed at the bottom of the washing kettle body 201, a filter plate 202 is further disposed in the washing kettle body 201, and a high pressure spray head 210 is further disposed at the upper portion of the washing kettle body 201.
Further, referring to fig. 2, the filtrate outlet of the washing kettle 201 is further connected to a vacuum box, the top of the vacuum box is further provided with a vacuum pipe port 203 connected to an external vacuum device, the bottom of the vacuum box is further provided with a washing liquid outlet 204 capable of being opened and closed, and the washing liquid outlet 204 is further connected to a waste liquid tank 209.
Further, referring to fig. 2, the filter plate 202 includes a filter frame and a filter element 205 disposed on the filter frame and capable of moving laterally along the surface thereof, a passage door 206 is disposed on the side of the washing tank 201, and when the passage door 206 is opened, a suction filtration discharge port for removing the filter element 205 is formed.
In some embodiments, please refer to fig. 3 again, the drying component 3 includes an inlet bin 32, a roller 33 and an outlet bin 35 which are sequentially communicated, two ends of the roller 33 are respectively connected with the inlet bin 32 and the outlet bin 35 in a rotating and sealing manner, a heating element 34 is further disposed on the outer surface of the roller 33, a funnel-shaped openable and closable drying material inlet is further disposed at the top of the inlet bin 32, and an openable and closable drying material outlet is further disposed at the bottom of the outlet bin 35.
Further, referring to fig. 3, the inlet bin 32 is further provided with a vacuum machine 31.
Furthermore, the ports of the drum 33, which are respectively communicated with the inlet bin 32 and the outlet bin 35, are also provided with openable baffles, and after the vacuum pumping is completed, the baffles are closed, so that the powder in the drum 33 can be conveniently dried.
The second technical scheme of the invention provides a preparation process of graphene oxide composite superfine silver powder, which is implemented by adopting the device, and the preparation process comprises the following steps:
(1) dissolving gum arabic and ascorbic acid in deionized water at 50 ℃ to prepare a reducing solution, and then feeding the reducing solution into the reaction kettle body 101 from an ascorbic acid feed inlet 105;
(2) atomizing and spraying the prepared silver nitrate solution from a silver nitrate feed inlet 104 into the reaction kettle body 101;
(3) opening a first stirring piece 103 and a hot water circulation pipeline in the reaction kettle body 101 for reaction, sending the obtained product into the suction filtration washing component 2 from a reaction outlet 106, and washing away excessive Arabic gum and unreacted ions by using water as a detergent;
(4) after the leaching and washing are finished, taking out the obtained silver powder, adding water to prepare a silver powder suspension, sending the silver powder suspension into the reaction kettle body 101 of the other reaction kettle assembly 1 through the ascorbic acid feed port 105, simultaneously adding the prepared GO solution into the reaction kettle body 101, and continuously stirring and heating for reaction;
(5) and (5) conveying the reaction product obtained in the step (4) into a suction filtration washing component 2, washing by adopting water and absolute ethyl alcohol, and conveying the obtained solid into a drying component 3 for drying to obtain the target product.
Specifically, the ascorbic acid solution is firstly injected into the reaction kettle body 101 through a reducing agent inlet (namely an ascorbic acid feed inlet 105) on a detachable kettle cover of the reaction kettle body 101 by using an infusion pump, then the silver nitrate solution is injected into a silver nitrate feed inlet 104 on the detachable kettle cover through the infusion pump, an automatic metering device is arranged on the silver nitrate feed inlet 104, the feeding time and the feeding amount of different reactions can be adjusted, and an automatically telescopic inlet pipeline and a rotary spray header are adopted for adjusting according to actual conditions so as to adapt to different reaction systems. The silver nitrate solution is finely sprayed to enable the silver nitrate solution to be sprayed out rapidly in small quantity, the silver nitrate solution is fully contacted with the reducing liquid to generate silver crystal nuclei instantly, the first stirring piece 103 is additionally arranged to enable the crystal nuclei to be rapidly and uniformly distributed in the solution, and the crystal nuclei are slowly gathered and grow at a certain reaction temperature along with the continuous increase of the silver crystal nuclei, so that the superfine silver powder with uniform and moderate particle size required by the research can be obtained.
After the silver powder is prepared, a pneumatic discharge valve which is in contact with the reaction liquid and is subjected to alkylation treatment is arranged at a reaction outlet 106 below the reaction kettle body 101, and the pneumatic discharge valve can prevent the prepared superfine silver powder from being blocked, and the superfine silver powder enters a suction filtration washing stage. After the discharge of the superfine silver powder is finished, the inside of the kettle is thoroughly cleaned through the high-pressure water spray nozzle 107 on the detachable kettle cover, so that the normal operation of the next reaction is ensured. And after the superfine silver powder is prepared, the superfine silver powder is prepared into turbid liquid, the turbid liquid is added into the other reaction kettle body 101, the reaction kettle body 101 is stirred, a certain amount of GO solution is quickly sprayed into the reaction kettle body 101 through the silver nitrate feeding hole 104, the GO solution and the superfine silver powder are in full contact reaction, and after the reaction is finished, the GO/superfine silver powder compound is discharged and sent to a suction filtration washing stage.
The suction filtration washing device of design lets in the washing kettle body 201 through the compound superfine silver powder turbid liquid of suction filtration inlet 207 with the oxidation graphite alkene of accomplishing of preparation in, the vacuum pump passes through vacuum pipe mouth 203 and becomes the vacuum state with the inside pumping of device, suction filtration washing efficiency of the compound superfine silver powder of oxidation graphite alkene with higher speed, the pressure of high pressure nozzle 210 is adjustable 360 rotatory in 0-150MPa, the water supply speed when guaranteeing the washing and can rinse the washing kettle body 201 inside after the washing, improve the washing efficiency of the compound superfine silver powder of oxidation graphite alkene through second stirring piece 208. After the waste liquid reaches a certain degree, the waste liquid can be discharged into the waste liquid tank 209 through the washing liquid outlet 204, and then purified for recycling at a later stage. After the graphene oxide composite superfine silver powder is washed, the access door 206 is opened, and the filter cake on the movable filter element 205, namely the graphene oxide composite superfine silver powder, is pulled out to enter the next stage.
Compound superfine silver powder of graphite alkene gets into from import storehouse 32, be equipped with the dry feed inlet that leaks hopper-shaped on the import storehouse 32, it is more convenient to make reinforced, the feeding is accomplished, seal whole device, open vacuum machine 31, make silver powder be in the vacuum state in drying process, open cylinder 33 and get into the rotation state, it dries to open heating member 34, compound superfine silver powder of oxidation graphite alkene can thermally equivalent in cylinder 33, under the vacuum state, avoid silver powder at the gathering of drying process, thereby keep the inherent characteristic of particle and can effectively improve oven-dry mass and drying efficiency.
The above embodiments may be implemented individually, or in any combination of two or more.
The above embodiments will be described in more detail with reference to specific examples.
Example 1:
the embodiment provides a preparation device of compound superfine silver powder of graphene oxide, and its structure is shown in fig. 1-3, including reation kettle subassembly 1, suction filtration washing subassembly 2 and drying assembly 3, wherein, reation kettle subassembly 1 establish the reation kettle body 101 of intermediate layer 102 in including, still be equipped with on reation kettle body 101 and stretch into its inside first stirring piece 103, the upper portion of reation kettle body 101 still is equipped with silver nitrate feed inlet 104 and ascorbic acid feed inlet 105, the lower part of reation kettle body 101 still be equipped with and connect the reaction outlet 106 of suction filtration washing subassembly 2. Preferably, a rotary spray head is further arranged at the silver nitrate feeding hole 104.
Referring to fig. 1 again, the reaction kettle body 101 is further provided with a high pressure water jet 107 connected to an external water supply device.
Referring to fig. 1 again, an interlayer 102 is disposed on a side wall of the reaction kettle body 101, and a hot water inlet 108 and a hot water outlet 109 connected to an external hot water circulation pipeline are further disposed on the interlayer 102.
Referring to fig. 1 again, a thermometer 110 is further disposed on the reaction vessel 101 and extends into the reaction vessel.
Referring to fig. 2 again, the suction filtration washing assembly 2 includes a closed washing kettle body 201, a suction filtration liquid inlet 207 is further disposed at the top of the washing kettle body 201, a filtrate outlet is further disposed at the bottom of the washing kettle body 201, a filter plate 202 is further disposed in the washing kettle body 201, and a high pressure nozzle 210 is further disposed at the upper portion of the washing kettle body 201.
Referring to fig. 2 again, the filtrate outlet of the washing kettle 201 is further connected to a vacuum box, the top of the vacuum box is further provided with a vacuum pipe port 203 connected to an external vacuum device, the bottom of the vacuum box is further provided with a washing liquid outlet 204 capable of being opened and closed, and the washing liquid outlet 204 is further connected to a waste liquid tank 209.
Referring to fig. 2 again, the filter plate 202 includes a filter frame and a filter element 205 disposed on the filter frame and capable of moving laterally along the surface thereof, a passage door 206 is further disposed on the side of the washing tank 201, and when the passage door 206 is opened, a suction filtration discharge port capable of taking out the filter element 205 is formed.
Referring to fig. 3 again, the drying assembly 3 includes an inlet bin 32, a drum 33 and an outlet bin 35 which are sequentially communicated, two ends of the drum 33 are respectively connected with the inlet bin 32 and the outlet bin 35 in a rotating and sealing manner, a heating element 34 is further disposed on the outer surface of the drum 33, a funnel-shaped openable and closable drying feed inlet is further disposed at the top of the inlet bin 32, and an openable and closable drying discharge outlet is further disposed at the bottom of the outlet bin 35.
Referring to fig. 3 again, the inlet bin 32 is further provided with a vacuum machine 31. The drum 33 is also provided with a baffle plate which can be opened and closed at the port communicated with the inlet bin 32 and the outlet bin 35 respectively, and the baffle plate is closed after the vacuum pumping is finished so as to conveniently dry the powder in the drum 33.
Example 2:
based on the preparation apparatus of embodiment 1, this embodiment also provides a preparation process of the graphene oxide composite ultrafine silver powder, which specifically includes the following steps:
(1) dissolving gum arabic and ascorbic acid in deionized water at 50 ℃ to prepare a reducing solution, and then feeding the reducing solution into the reaction kettle body 101 from an ascorbic acid feed inlet 105;
(2) atomizing and spraying the prepared silver nitrate solution from a silver nitrate feed inlet 104 into the reaction kettle body 101;
(3) opening a first stirring piece 103 and a hot water circulation pipeline in the reaction kettle body 101 for reaction, sending the obtained product into the suction filtration washing component 2 from a reaction outlet 106, and washing away excessive Arabic gum and unreacted ions by using water as a detergent;
(4) after the leaching and washing are finished, taking out the obtained silver powder, adding water to prepare a silver powder suspension, sending the silver powder suspension into the reaction kettle body 101 of the other reaction kettle assembly 1 through the ascorbic acid feed port 105, simultaneously adding the prepared GO solution into the reaction kettle body 101, and continuously stirring and heating for reaction;
(5) and (5) conveying the reaction product obtained in the step (4) into a suction filtration washing component 2, washing by adopting water and absolute ethyl alcohol, and conveying the obtained solid into a drying component 3 for drying to obtain the target product.
Specifically, with reference to fig. 1 to 3, in this embodiment, an ascorbic acid solution is first injected into the reaction kettle body 101 through a reducing agent inlet (i.e., an ascorbic acid feed port 105) on a detachable kettle cover of the reaction kettle body 101 by using an infusion pump, and then a silver nitrate solution is injected into a silver nitrate feed port 104 on the detachable kettle cover by using the infusion pump, wherein an automatic metering device is arranged on the silver nitrate feed port 104, so that the feeding time and feeding amount of different reactions can be adjusted, and an automatically retractable feed-in pipeline and a rotary spray header are adopted, so that the adjustment can be performed according to actual conditions to adapt to different reaction systems. The silver nitrate solution is finely sprayed to enable the silver nitrate solution to be sprayed out rapidly in small quantity, the silver nitrate solution is fully contacted with the reducing liquid to generate silver crystal nuclei instantly, the first stirring piece 103 is additionally arranged to enable the crystal nuclei to be rapidly and uniformly distributed in the solution, and the crystal nuclei are slowly gathered and grow at a certain reaction temperature along with the continuous increase of the silver crystal nuclei, so that the superfine silver powder with uniform and moderate particle size required by the research can be obtained.
After the silver powder is prepared, a pneumatic discharge valve which is in contact with the reaction liquid and is subjected to alkylation treatment is arranged at a reaction outlet 106 below the reaction kettle body 101, and the pneumatic discharge valve can prevent the prepared superfine silver powder from being blocked, and the superfine silver powder enters a suction filtration washing stage. After the discharge of the superfine silver powder is finished, the inside of the kettle is thoroughly cleaned through the high-pressure water spray nozzle 107 on the detachable kettle cover, so that the normal operation of the next reaction is ensured. And after the superfine silver powder is prepared, the superfine silver powder is prepared into turbid liquid, the turbid liquid is added into the other reaction kettle body 101, the reaction kettle body 101 is stirred, a certain amount of GO solution is quickly sprayed into the reaction kettle body 101 through the silver nitrate feeding hole 104, the GO solution and the superfine silver powder are in full contact reaction, and after the reaction is finished, the GO/superfine silver powder compound is discharged and sent to a suction filtration washing stage.
The suction filtration washing device of design lets in the washing kettle body 201 through the compound superfine silver powder turbid liquid of suction filtration inlet 207 with the oxidation graphite alkene of accomplishing of preparation in, the vacuum pump passes through vacuum pipe mouth 203 and becomes the vacuum state with the inside pumping of device, suction filtration washing efficiency of the compound superfine silver powder of oxidation graphite alkene with higher speed, the pressure of high pressure nozzle 210 is adjustable 360 rotatory in 0-150MPa, the water supply speed when guaranteeing the washing and can rinse the washing kettle body 201 inside after the washing, improve the washing efficiency of the compound superfine silver powder of oxidation graphite alkene through second stirring piece 208. After the waste liquid reaches a certain degree, the waste liquid can be discharged into the waste liquid tank 209 through the washing liquid outlet 204, and then purified for recycling at a later stage. After the graphene oxide composite superfine silver powder is washed, the access door 206 is opened, and the filter cake on the movable filter element 205, namely the graphene oxide composite superfine silver powder, is pulled out to enter the next stage.
Compound superfine silver powder of graphite alkene gets into from import storehouse 32, be equipped with the dry feed inlet that leaks hopper-shaped on the import storehouse 32, it is more convenient to make reinforced, the feeding is accomplished, seal whole device, open vacuum machine 31, make silver powder be in the vacuum state in drying process, open cylinder 33 and get into the rotation state, it dries to open heating member 34, compound superfine silver powder of oxidation graphite alkene can thermally equivalent in cylinder 33, under the vacuum state, avoid silver powder at the gathering of drying process, thereby keep the inherent characteristic of particle and can effectively improve oven-dry mass and drying efficiency.
Fig. 4 and 5 are SEM and FESEM photographs of the composite ultrafine silver powder prepared in this example, and it can be seen that the composite ultrafine silver powder prepared in this example has relatively uniform particle size.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The utility model provides a preparation facilities of compound superfine silver powder of graphite oxide, its characterized in that, includes the reation kettle subassembly, suction filtration washing subassembly and dry subassembly, wherein, the reation kettle subassembly include the reation kettle body, still be equipped with the first stirring piece that stretches into its inside on the reation kettle body, the upper portion of the reation kettle body still is equipped with silver nitrate feed inlet and ascorbic acid feed inlet, the lower part of the reation kettle body still be equipped with the connection the reaction outlet of suction filtration washing subassembly.
2. The apparatus for preparing the graphene oxide-silver superfine powder according to claim 1, wherein the reaction vessel body is further provided with a high-pressure water jet connected with an external water supply device.
3. The apparatus according to claim 1, wherein the side wall of the reaction vessel body is provided with an interlayer, and the interlayer is further provided with a hot water inlet and a hot water outlet for connecting an external hot water circulation pipeline.
4. The apparatus for preparing the graphene oxide-silver ultrafine powder according to claim 1, wherein a thermometer is further disposed on the reaction vessel body and extends into the reaction vessel body.
5. The apparatus according to claim 1, wherein the suction filtration washing assembly comprises a closed washing vessel, a suction filtration liquid inlet is further disposed at the top of the washing vessel, a filtrate outlet is further disposed at the bottom of the washing vessel, a filter plate is further disposed in the washing vessel, and a high pressure nozzle is further disposed at the upper portion of the washing vessel.
6. The apparatus according to claim 5, wherein the filtrate outlet of the washing vessel is further connected to a vacuum chamber, the top of the vacuum chamber is further provided with a vacuum line port connected to an external vacuum device, the bottom of the vacuum chamber is further provided with an openable washing outlet, and the washing outlet is further connected to a waste liquid tank.
7. The apparatus according to claim 5, wherein the filter plate comprises a filter frame and a filter element disposed on the filter frame and movable laterally along the surface thereof, and a port door is disposed on a side of the washing vessel, and the port door forms a suction outlet for removing the filter element when opened.
8. The device for preparing the graphene oxide composite ultrafine silver powder according to claim 1, wherein the drying component comprises an inlet bin, a roller and an outlet bin which are sequentially communicated, two ends of the roller are respectively connected with the inlet bin and the outlet bin in a rotating and sealing manner, a heating element is further arranged on the outer surface of the roller, a funnel-shaped openable drying feed inlet is further formed in the top of the inlet bin, and an openable drying discharge outlet is further formed in the bottom of the outlet bin.
9. The apparatus for preparing the graphene oxide-silver superfine powder according to claim 8, wherein the inlet bin is further provided with a vacuum machine.
10. A process for preparing graphene oxide composite ultrafine silver powder, which is implemented by using the apparatus according to any one of claims 1 to 9, wherein the process comprises the following steps:
(1) dissolving gum arabic and ascorbic acid in deionized water at 50 ℃ to prepare a reducing solution, and then feeding the reducing solution into a reaction kettle body from an ascorbic acid feed inlet;
(2) then, atomizing and spraying the prepared silver nitrate solution from a silver nitrate feed inlet into the reaction kettle body;
(3) opening a first stirring piece and a hot water circulation pipeline in the reaction kettle body, reacting, conveying the obtained product into a suction filtration washing component from a reaction outlet, and washing off redundant gum arabic and unreacted ions by using water as a detergent;
(4) after the leaching and washing are finished, taking out the obtained silver powder, adding water to prepare a silver powder suspension, sending the silver powder suspension into a reaction kettle body of another reaction kettle component through an ascorbic acid feed port, simultaneously adding the prepared GO solution into the reaction kettle body, and continuously stirring and heating for reaction;
(5) and (5) conveying the reaction product obtained in the step (4) into a suction filtration washing assembly, washing by using water and absolute ethyl alcohol, and conveying the obtained solid into a drying assembly for drying to obtain the target product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110266091.3A CN113385125A (en) | 2021-03-11 | 2021-03-11 | Preparation device and process of graphene oxide composite superfine silver powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110266091.3A CN113385125A (en) | 2021-03-11 | 2021-03-11 | Preparation device and process of graphene oxide composite superfine silver powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113385125A true CN113385125A (en) | 2021-09-14 |
Family
ID=77617479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110266091.3A Pending CN113385125A (en) | 2021-03-11 | 2021-03-11 | Preparation device and process of graphene oxide composite superfine silver powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113385125A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203264376U (en) * | 2013-04-27 | 2013-11-06 | 河北钢铁股份有限公司邯郸分公司 | Suction filtration device |
| WO2016145985A1 (en) * | 2015-03-18 | 2016-09-22 | 上海和伍复合材料有限公司 | Graphene/silver composite material and preparation method thereof |
| CN106683740A (en) * | 2017-03-16 | 2017-05-17 | 西北大学 | Hydrothermal method based graphene coated sliver powder preparation and graphene coated silver powder modified lead-free paste preparation method |
| CN206688691U (en) * | 2017-05-10 | 2017-12-01 | 新乡市锦源化工有限公司 | Prepare the reactor and system of sulfamic acid |
| CN109387039A (en) * | 2017-08-03 | 2019-02-26 | 程长春 | Rotary-drum vacuum dryer |
| CN211462268U (en) * | 2019-12-26 | 2020-09-11 | 广东也乐新材料制造有限公司 | Vacuum suction filtration integrated device |
-
2021
- 2021-03-11 CN CN202110266091.3A patent/CN113385125A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203264376U (en) * | 2013-04-27 | 2013-11-06 | 河北钢铁股份有限公司邯郸分公司 | Suction filtration device |
| WO2016145985A1 (en) * | 2015-03-18 | 2016-09-22 | 上海和伍复合材料有限公司 | Graphene/silver composite material and preparation method thereof |
| CN106683740A (en) * | 2017-03-16 | 2017-05-17 | 西北大学 | Hydrothermal method based graphene coated sliver powder preparation and graphene coated silver powder modified lead-free paste preparation method |
| CN206688691U (en) * | 2017-05-10 | 2017-12-01 | 新乡市锦源化工有限公司 | Prepare the reactor and system of sulfamic acid |
| CN109387039A (en) * | 2017-08-03 | 2019-02-26 | 程长春 | Rotary-drum vacuum dryer |
| CN211462268U (en) * | 2019-12-26 | 2020-09-11 | 广东也乐新材料制造有限公司 | Vacuum suction filtration integrated device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5784465B2 (en) | Filtration dryer | |
| CN111841423B (en) | Temperature-adjustable graphene processing equipment and use method | |
| CN113769433B (en) | Production line and method for efficiently producing fried burdock formula particles | |
| CN210332808U (en) | Raw material crushing device for metal silicon purification | |
| CN112968164A (en) | Experimental method for preparing lithium battery positive electrode material precursor | |
| CN212090976U (en) | A filter equipment for piperic acid crystallization | |
| CN113385125A (en) | Preparation device and process of graphene oxide composite superfine silver powder | |
| CN109569511A (en) | Acid washed activated Carbon fibe and active carbon loading silver fiber producing processes and filter/circle | |
| CN212701227U (en) | Solvent recovery device containing waste gas of thionyl chloride, dichloromethane and n-heptane | |
| CN216367732U (en) | Rare earth heat-resistant coating pretreatment preparation device | |
| CN207891059U (en) | A kind of process units of nano hydrotalcite | |
| CN210906157U (en) | Pyrolytic reaction cauldron of lithium carbonate production usefulness | |
| CN211897392U (en) | Warp color mixing device of dyeing and sizing combination machine | |
| CN218689198U (en) | Heating dissolving kettle device for PVB production raw materials | |
| CN210710788U (en) | Device for preparing magnetic nano ferroferric oxide | |
| CN217221479U (en) | Condensation reaction device is used in preparation of sulfadoxine | |
| CN220110803U (en) | Plant growth regulator triacontanol dissolving device | |
| CN109894447A (en) | A kind of automatic tank cleaning device of hydrolytic decomposition pot and its cleaning of evaporator method | |
| CN220213939U (en) | Evaporation circulating device of sodium formate double-effect evaporator | |
| CN220845509U (en) | Active copper oxide activity controllable sterilizing, cleaning and recycling device | |
| CN218077533U (en) | Chloride solution hydrolysis and precipitation device | |
| CN215611568U (en) | Polymerization reactor is used in water-reducing agent production | |
| CN217246894U (en) | Extraction element is used to clear granule | |
| CN219942842U (en) | Environment-friendly chemical synthesis kettle | |
| CN218795802U (en) | Integrated device for preparing superfine silver-coated copper powder |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210914 |