CN111992037A - Forward osmosis hydrogel draw solution, preparation method and application thereof - Google Patents
Forward osmosis hydrogel draw solution, preparation method and application thereof Download PDFInfo
- Publication number
- CN111992037A CN111992037A CN201910445512.1A CN201910445512A CN111992037A CN 111992037 A CN111992037 A CN 111992037A CN 201910445512 A CN201910445512 A CN 201910445512A CN 111992037 A CN111992037 A CN 111992037A
- Authority
- CN
- China
- Prior art keywords
- solution
- hydrogel
- forward osmosis
- carrier
- draw solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
- B01D61/005—Osmotic agents; Draw solutions
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a forward osmosis hydrogel drawing liquid, which comprises a carrier and a solution adsorbed on the carrier, wherein the solution comprises the following components in parts by weight: 10-20% of N-isopropylacrylamide (NIPAM); 0.1-0.5% of N, N' -Methylene Bisacrylamide (MBA); 0.5-1% of Sodium Acrylate (SA); 40-50% of water; 30-40% of sodium polystyrene sulfonate (PSSS) aqueous solution; 0.1-0.5% of ammonium persulfate. The invention also provides a preparation method of the gel and application of the gel in the field of wastewater desalination. When low-temperature waste heat can be utilized, the regeneration cost of the drawing liquid can be greatly reduced, so that the operation cost of the whole forward osmosis process is reduced, and the forward osmosis process is favorably promoted to be engineered.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a hydrogel drawing liquid and a preparation method thereof, which can be applied to the field of wastewater desalination.
Background
Forward Osmosis (FO) is a natural phenomenon, and is a new membrane separation technology driven by concentration developed in recent years, and is a membrane separation process driven only by osmotic pressure without external pressure as a driving force. In forward osmosis processes, water flows from a region on the higher water chemical potential (or lower osmotic pressure) side through a permselective membrane to a region on the lower water chemical potential (or higher osmotic pressure) side. Unlike the reverse osmosis process, the driving force for the forward osmosis process is osmotic pressure, not applied pressure.
No external pressure is applied in the forward osmosis process, and the membrane pollution is low because the membrane material has hydrophilicity; can be applied to separation processes which cannot be applied by the traditional reverse osmosis technology, such as dyeing wastewater, advanced treatment of garbage penetrating fluid and a membrane bioreactor.
The driving force of the forward osmosis membrane process is the osmotic pressure difference between the draw solution and the feed solution. To realize forward osmosis membrane processes, even to expand the production capacity, the effect of the draw solution is of great importance. Therefore, the selection and constitution of the drawing liquid are also important research subjects, and a good drawing liquid should satisfy the following conditions:
(1) sufficient osmotic pressure difference exists between the drawing liquid and the raw material liquid, so that pure water continuously permeates through the drawing liquid;
(2) the draw solution should be easy to recover, easily concentrated or separated by relevant methods to obtain pure water and maintain forward osmotic driving force;
(3) the draw solution should be inert, stable, (nearly) neutral, non-toxic (no toxic effects to humans and the environment), reasonably priced;
(4) the membrane cannot be damaged by chemical means such as reaction and dissolution and physical means such as pollution by the drawing liquid;
(5) the back diffusion capacity of the drawing liquid is as low as possible, so that the consumption of the drawing liquid and the pollution to raw water are reduced;
(6) the viscosity is low even at high concentrations.
Therefore, finding a suitable draw solution is very important, but very difficult.
Depending on the type, the draw solution can be classified into a gas and volatile type, an inorganic type, an organic type, and a novel synthetic compound type. Different types of draw solutions each have advantages and disadvantages: the gas and volatile draw solutions have limited osmotic pressure, limited recoverability, and back diffusion; the inorganic draw solution has high osmotic pressure and high flux, but the recovery price is expensive and the back diffusion exists; the organic draw solution has the advantages of high osmotic pressure, high flux and the like, but has high recovery price and back diffusion; the advantages of the composite organic-inorganic nanoparticles are high osmotic pressure, high flux and easy regeneration, and the disadvantages are that whether the nanoparticles are harmful to human health and environment is still to be evaluated.
So far, no draw solution can meet the characteristics of an ideal draw solution, which is also an important reason for restricting the development of forward osmosis process.
Disclosure of Invention
Therefore, the object of the present invention is to provide a semisolid hydrogel extraction solution. Another technical problem to be solved by the present invention is to provide a method for preparing the hydrogel extraction solution.
The technical scheme of the invention is that a forward osmosis hydrogel draw solution,
the hydrogel drawing liquid comprises a carrier and a solution adsorbed on the carrier, wherein the solution comprises the following components in parts by weight:
n-isopropylacrylamide (NIPAM) and Sodium Acrylate (SA) are monomers for preparing hydrogel, N, N' -Methylenebisacrylamide (MBA) is a connecting agent for preparing hydrogel, Ammonium Persulfate (APS) is an initiator for preparing hydrogel, and a sodium polystyrene sulfonate aqueous solution is a coagulant for preparing hydrogel.
In a forward osmosis hydrogel draw solution according to the present invention, the carrier is preferably a porous medium with strong adsorption capacity.
According to a forward osmosis hydrogel draw solution of the present invention, further, the carrier is a sponge.
A forward osmosis hydrogel draw solution according to the present invention, preferably the concentration of the aqueous solution of sodium polystyrene sulfonate (PSSS) is 20-40 wt.%. More preferably, the concentration of the aqueous solution of sodium polystyrene sulfonate (PSSS) is 25 to 32 wt%.
The invention also provides a preparation method of the forward osmosis hydrogel draw solution,
(1) dividing the carrier into suitable shapes for standby;
(2) sequentially dissolving N-isopropylacrylamide (NIPAM), N' -Methylenebisacrylamide (MBA) and Sodium Acrylate (SA) in water according to the component ratio; after the reactants are dissolved, adding a sodium polystyrene sulfonate (PSSS) aqueous solution, and finally adding Ammonium Persulfate (APS);
(3) adding the solution prepared in the step (2) into the carrier in the step (1);
(4) and (3) placing the carrier and the solution in a closed container, then placing the container in an oven, raising the temperature to 40-75 ℃, and keeping the temperature until the liquid does not flow any more.
(5) And cooling to obtain the hydrogel drawing liquid.
And (3) uniformly stirring in the step (2).
According to a method of preparing a forward osmosis hydrogel draw solution according to the present invention, preferably the carrier is a sponge.
According to the method for preparing a forward osmosis hydrogel draw solution of the present invention, preferably, in the step (3), the addition is dropping.
According to the method of preparing a forward osmosis hydrogel draw solution of the present invention, it is preferable that the solution added in step (3) just soaks the support.
According to the preparation method of the forward osmosis hydrogel draw-up solution, the constant temperature time in the step (4) is preferably 60-150 min.
According to the preparation method of the forward osmosis hydrogel draw solution, the temperature is preferably increased to 55-75 ℃ in the step (5). Namely, the hydrogel production temperature is preferably 55 to 75 ℃.
The invention also provides application of the forward osmosis hydrogel draw solution in the field of wastewater desalination.
The macromolecular chain of poly N-isopropyl acrylamide (PNIPAM) in the hydrogel simultaneously has hydrophilic amido and hydrophobic isopropyl, so that the crosslinked PNIPAM hydrogel has temperature-sensitive characteristic. The substance is hydrophilic at normal temperature, has water absorption capacity and higher osmotic pressure, and can absorb water penetrating through the forward osmosis membrane; after the temperature of the hydrogel is raised to 40 ℃ by warm water circulation above 40 ℃ (the temperature is the running temperature of the hydrogel in the forward osmosis process), the hydrogel is hydrophobic, and water absorbed at normal temperature can be released to complete regeneration of the hydrogel.
The invention has the beneficial effects that:
the invention provides a forward osmosis hydrogel draw solution and a preparation method thereof. The hydrogel can absorb water at normal temperature, and the hydrogel with the temperature of more than 40 ℃ can release the water absorbed at normal temperature to complete the regeneration of the hydrogel. The traditional inorganic salt drawing liquid generally has reverse salt diffusion, namely the drawing liquid can penetrate through a forward osmosis membrane to enter the wastewater side to be treated, so that on one hand, the loss of the drawing liquid is caused, on the other hand, the salt content in the wastewater to be treated is increased, and the subsequent treatment and utilization are not facilitated; when the hydrogel is used as a draw solution, the hydrogel is a high molecular polymer and is semisolid, so that the problem of reverse salt diffusion of the draw solution is completely solved; the produced water of the hydrogel can be directly recycled without further treatment. When low-temperature waste heat can be utilized, the regeneration cost of the drawing liquid can be greatly reduced, so that the operation cost of the whole forward osmosis process is reduced, and the forward osmosis process is favorably promoted to be engineered.
Drawings
FIG. 1 is a graph showing the results of the water absorption and dehydration performances of the hydrogel in example 1 of the present invention.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
(1) The carrier is sponge, and the sponge is cut into a shape with a diameter of 5cm and a thickness of 7mm
(2) 2g of N-isopropylacrylamide (NIPAM), 0.035g of N, N' -Methylenebisacrylamide (MBA) and 0.1g of Sodium Acrylate (SA) were dissolved in this order in 7ml of water; after the reactants were dissolved, 5.5g of sodium polystyrene sulfonate (PSSS) aqueous solution (35% by mass concentration) was added, and finally 0.04g of Ammonium Persulfate (APS) was added
(3) And (3) dripping the prepared solution in the step (2) into the sponge in the step (1), and just soaking the sponge with the added solution.
(4) Placing the sponge and the solution in a sealed container, placing in an oven, heating the oven to 65 deg.C, and maintaining the temperature until the liquid does not flow for 150 min.
(5) And cooling to obtain the hydrogel drawing liquid.
Example 2
(1) The carrier is sponge, and the sponge is cut into a shape with a diameter of 5cm and a thickness of 7mm
(2) Dissolving 1.5g of N-isopropylacrylamide (NIPAM), 0.035g of N, N' -Methylenebisacrylamide (MBA) and 0.05g of Sodium Acrylate (SA) in 7ml of water in this order; after the reactants were dissolved, 4.5g of sodium polystyrene sulfonate (PSSS) aqueous solution (30% by mass concentration) was added, and finally 0.04g of Ammonium Persulfate (APS) was added
(3) And (3) dripping the prepared solution in the step (2) into the sponge in the step (1), and just soaking the sponge with the added solution.
(4) Placing the sponge and the solution in a sealed container, placing in an oven, heating the oven to 65 deg.C, and maintaining the temperature until the liquid does not flow for 150 min.
(5) And cooling to obtain the hydrogel drawing liquid.
Example 3
(1) The carrier was a sponge, and the sponge was cut into a shape of 5cm in diameter and 7mm in thickness.
(2) 2.5g of N-isopropylacrylamide (NIPAM), 0.04g of N, N' -Methylenebisacrylamide (MBA) and 0.1g of Sodium Acrylate (SA) were dissolved in this order in 7ml of water; after the reactants were dissolved, 5g of sodium polystyrene sulfonate (PSSS) aqueous solution (40% by mass concentration) was added, and finally 0.04g of Ammonium Persulfate (APS) was added.
(3) And (3) dripping the prepared solution in the step (2) into the sponge in the step (1), and just soaking the sponge with the added solution.
(4) Placing the sponge and the solution in a sealed container, placing in an oven, heating the oven to 70 deg.C, and maintaining the temperature until the liquid does not flow for 120 min.
(5) And cooling to obtain the hydrogel drawing liquid.
Performance test
The hydrogel draw-up solution obtained in example 1 was subjected to water absorption and dehydration performance tests, and the results are shown in FIG. 1. The test water used was a sodium chloride solution with a salt content of 2000 mg/L. The hydrogel was tested for water absorption and dehydration performance in both Forward Osmosis (FO) and pressure damped osmosis (PRO) states. It can be seen that the hydrogels of the present invention have good water absorption and dehydration properties in both FO and PRO states, and the water absorption and dehydration properties of the hydrogels do not decrease after cycling.
Claims (10)
1. A forward osmosis hydrogel draw solution, comprising:
the hydrogel drawing liquid comprises a carrier and a solution adsorbed on the carrier, wherein the solution comprises the following components in parts by weight:
2. the forward osmosis hydrogel draw solution of claim 1, wherein: the carrier is a porous medium with strong adsorption capacity.
3. A forward osmosis hydrogel draw solution according to claim 2, wherein: the carrier is sponge.
4. The forward osmosis hydrogel draw solution of claim 1, wherein: the concentration of the sodium polystyrene sulfonate (PSSS) aqueous solution is 20-40 wt.%.
5. A method of preparing a forward osmosis hydrogel draw solution as claimed in claim 1, comprising:
(1) dividing the carrier into suitable shapes for standby;
(2) sequentially dissolving N-isopropylacrylamide (NIPAM), N' -Methylenebisacrylamide (MBA) and Sodium Acrylate (SA) in water according to the component ratio; after the reactants are dissolved, adding a sodium polystyrene sulfonate (PSSS) aqueous solution, and finally adding Ammonium Persulfate (APS);
(3) adding the solution prepared in the step (2) into the carrier in the step (1);
(4) and (3) placing the carrier and the solution in a closed container, then placing the container in an oven, raising the temperature to 40-75 ℃, and keeping the temperature until the liquid does not flow any more.
(5) And cooling to obtain the hydrogel drawing liquid.
6. The method of claim 5, wherein the method comprises the steps of: the carrier is a sponge.
7. The method of claim 5, wherein the method comprises the steps of: in the step (3), the adding is dropping; and (4) just soaking the carrier by the solution added in the step (3).
8. The method of claim 5, wherein the method comprises the steps of: and (4) keeping the constant temperature for 60-150 min.
9. The method of claim 5, wherein the method comprises the steps of: in the step (5), the temperature is increased to 55-75 ℃.
10. Use of the forward osmosis hydrogel draw solution of claim 1 in the field of desalination of wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910445512.1A CN111992037A (en) | 2019-05-27 | 2019-05-27 | Forward osmosis hydrogel draw solution, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910445512.1A CN111992037A (en) | 2019-05-27 | 2019-05-27 | Forward osmosis hydrogel draw solution, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111992037A true CN111992037A (en) | 2020-11-27 |
Family
ID=73461670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910445512.1A Pending CN111992037A (en) | 2019-05-27 | 2019-05-27 | Forward osmosis hydrogel draw solution, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111992037A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100370A (en) * | 2021-11-29 | 2022-03-01 | 中新国际联合研究院 | Forward osmosis and draw liquid regeneration modular device using temperature-sensitive hydrogel as draw liquid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492261A (en) * | 2015-01-13 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Forward osmosis separation method, application of sodium polystyrenesulfonate and recovery method |
| CN104841288A (en) * | 2015-04-30 | 2015-08-19 | 天津工业大学 | Composite microgel membrane for CO2/N2 gas separation and preparation method thereof |
| US20160082391A1 (en) * | 2013-04-26 | 2016-03-24 | Nanyang Technological University | A draw solute and an improved forward osmosis method |
| CN106587271A (en) * | 2016-11-30 | 2017-04-26 | 大连理工大学 | Cleaning water drawing method using hydrophilic compression resistant aerogel as forward osmosis drawing substance |
| CN106925119A (en) * | 2017-03-10 | 2017-07-07 | 山东大学 | Poly-epoxy succinic acid is used as drawing application of the liquid in positive infiltration |
| CN108047377A (en) * | 2017-12-06 | 2018-05-18 | 四川警察学院 | A kind of temperature-sensitive hydrogel and preparation method thereof |
| CN108602016A (en) * | 2015-09-15 | 2018-09-28 | 宝山钢铁股份有限公司 | Material is drawn in positive infiltration |
-
2019
- 2019-05-27 CN CN201910445512.1A patent/CN111992037A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160082391A1 (en) * | 2013-04-26 | 2016-03-24 | Nanyang Technological University | A draw solute and an improved forward osmosis method |
| CN104492261A (en) * | 2015-01-13 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Forward osmosis separation method, application of sodium polystyrenesulfonate and recovery method |
| CN104841288A (en) * | 2015-04-30 | 2015-08-19 | 天津工业大学 | Composite microgel membrane for CO2/N2 gas separation and preparation method thereof |
| CN108602016A (en) * | 2015-09-15 | 2018-09-28 | 宝山钢铁股份有限公司 | Material is drawn in positive infiltration |
| CN106587271A (en) * | 2016-11-30 | 2017-04-26 | 大连理工大学 | Cleaning water drawing method using hydrophilic compression resistant aerogel as forward osmosis drawing substance |
| CN106925119A (en) * | 2017-03-10 | 2017-07-07 | 山东大学 | Poly-epoxy succinic acid is used as drawing application of the liquid in positive infiltration |
| CN108047377A (en) * | 2017-12-06 | 2018-05-18 | 四川警察学院 | A kind of temperature-sensitive hydrogel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| KHA L TU, ET AL.: ""Fast-responsive monolithic hydrogels as draw agent for forward osmosis membrane process"", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
| 孙晓君: ""多孔聚合物水凝胶的合成及正渗透性能"", 《高分子材料科学与工程》 * |
| 谌永红主编: "《给水排水工程》", 29 February 2008, 中国环境科学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100370A (en) * | 2021-11-29 | 2022-03-01 | 中新国际联合研究院 | Forward osmosis and draw liquid regeneration modular device using temperature-sensitive hydrogel as draw liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Forward osmosis using electric-responsive polymer hydrogels as draw agents: Influence of freezing–thawing cycles, voltage, feed solutions on process performance | |
| CN108579709B (en) | Porous structure elastic composite material for extracting uranium from seawater and preparation method thereof | |
| CN102614842B (en) | Chelate fiber adsorbent for extracting uranium from seawater and preparation method thereof | |
| CN105504166A (en) | Sodium alginate-acrylamide composite aquagel, and preparation method and application thereof | |
| Gawande et al. | Superabsorbent polymer (SAP) hydrogels for protein enrichment | |
| CN103936146B (en) | Preparation method and application of quinonoid compound modified nylon membrane biological carrier | |
| CN104841288A (en) | Composite microgel membrane for CO2/N2 gas separation and preparation method thereof | |
| CN101862604A (en) | Method for preparing hydrophilic porous membrane | |
| KR102058374B1 (en) | Radioactive cesium absorbent and method of the same | |
| US11826705B2 (en) | Apparatus and process for separation of water from dissolved solutes by forward osmosis | |
| CN103394295A (en) | Hydrophilic PVDF (Polyvinylidene Fluoride) composite ultrafiltration membrane and preparation method thereof | |
| CN111992037A (en) | Forward osmosis hydrogel draw solution, preparation method and application thereof | |
| CN105413664A (en) | Modified UHMW (Ultra High Molecular Weight) polyethylene fiber, and preparation method and application thereof | |
| CN105771700A (en) | Mixed diamine monomer adopted chlorine-resistant nanofiltration membrane and preparation method therefor | |
| CN113772667A (en) | Graphene oxide-based porous photothermal material capable of efficiently generating solar steam, and preparation method and application thereof | |
| CN112299578A (en) | Forward osmosis wastewater recycling method | |
| CN109304105B (en) | Forward osmosis membrane for efficiently adsorbing and removing heavy metal ions and preparation method and application thereof | |
| CN109110886B (en) | Cation exchange membrane for electrodialysis treatment of ammonia-nitrogen wastewater and preparation method | |
| CN107433192B (en) | A kind of composite fibre sorbing material and preparation method thereof | |
| CN113318598A (en) | Method for enhancing selective permeability of reverse osmosis membrane by adjusting pore diameter of base membrane | |
| CN105498546A (en) | Nano-conjugated polymer doping modified reverse osmosis composite membrane | |
| Li et al. | Removal of cationic dyes from aqueous solution by hydrophobically modified poly (acrylic acid) hydrogels | |
| CN104530307A (en) | Preparation of hydrophilic acrylic adsorption resin and application of acrylic adsorption resin in phenolic wastewater treatment | |
| CN112044275B (en) | Charge gradient hydrogel film for thermal seawater desalination and preparation method thereof | |
| CN116178783A (en) | Preparation method of temperature-sensitive hydrogel based on porous material framework |
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: 20201127 |