CN105617870A - Method for modifying ultrafiltration membrane through nano-particle coating - Google Patents
Method for modifying ultrafiltration membrane through nano-particle coating Download PDFInfo
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- CN105617870A CN105617870A CN201510971390.1A CN201510971390A CN105617870A CN 105617870 A CN105617870 A CN 105617870A CN 201510971390 A CN201510971390 A CN 201510971390A CN 105617870 A CN105617870 A CN 105617870A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- 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
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- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for modifying an ultrafiltration membrane through a nano-particle coating, and belongs to the field of environmental water treatment. The method comprises the following steps: adding A into deionized water, then adding a flocculant; regulating pH to be neutral through an acid solution or an alkaline solution after the reaction is complete; heating the solution to be boiled to enable amorphous flocs in the solution to be granulated, leaving the solution to stand to be naturally cooled to room temperature, and loading particles in the solution to the surface of the ultrafiltration membrane in a constant pressure condition. According to the method for modifying the ultrafiltration membrane through the nano-particle coating, ano-particles pre-deposited on the surface of the ultrafiltration membrane preferentially adsorb pollutants, so that membrane pollution is reduced, the service life of the membrane is prolonged, and the water treatment efficiency is improved; besides, physical absorption is formed between the nano-particles pre-deposited on the surface of the ultrafiltration membrane and the ultrafiltration membrane, after reaction, the nano-particles can be completely removed after being scraped through a plastic scraper and are washed with deionized water, therefore the ultrafiltration membrane can be reused, the method is simple and easy to operate, liable to large-scale application, and convenient for promotion.
Description
Technical field
The present invention relates to a kind of method that nanoparticle coating is modified to ultrafilter membrane, belong to environment-protective water process field.
Background technology
Membrane technology is more and more extensive in the application of environment-protective water process field, progressively become one of basis of world's strategy of sustainable development, membrane technology is considered as one of 21 century most important new technique, but, fouling membrane remains the major obstacle hindering membrane technology popularization and application. The method mainly taked to reduce fouling membrane of early stage is sewage to carry out a preprocessing process to reduce fouling membrane, main be also the most traditional preprocessing process be chemical coagulation. In addition, also has the method that film carried out the pretreatment such as ultrasonic, backwash, electricity flocculation, electricity coagulation. Ultrasonic some materials of film surface adsorption can only be removed, and the contaminant particle that cannot adsorb in fenestra is removed; Backwash has the ultrasonic better removal efficiency of ratio, the granule of absorption in fenestra can be removed, and although chemical flocculation, electricity flocculation and electricity these methods of coagulation can reduce fouling membrane to a certain extent, but the chemical reagent added all can cause fouling membrane, and pre-deposition processes and can be preferably minimized by the fouling membrane that chemical reagent causes, and preliminary sedimentation lamination is easily removed, it is possible not only to improve organic removal efficiency, it is also possible to reduce the decay of membrane flux.
Summary of the invention
It is an object of the invention to for existing for the deficiency in the process of ultrafiltration film water, propose a kind of method that nanoparticle coating is modified to ultrafilter membrane, the method at one layer of nano-particle of ultrafiltration membrane surface pre-deposition as pretreatment, for the pollutant retained and adsorb in water, to reduce the pollution of film to greatest extent.
It is an object of the invention to be achieved through the following technical solutions.
A kind of method that nanoparticle coating is modified to ultrafilter membrane, specifically comprises the following steps that and joins in deionized water by A, then add flocculant; The mol ratio of the addition of A and flocculant is 20:1-1:2; After reacting completely, regulate pH by acid solution or alkaline solution and become neutrality; Then by solution ebuillition of heated, the amorphous floc particle in solution is made, by solution left standstill to room temperature, under constant-pressure conditions, by the particulate load in solution to ultrafiltration membrane surface.
Described A includes: one or more in sodium bicarbonate, potassium bicarbonate, dibastic sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate.
Described flocculant be in aluminum sulfate, aluminum chloride, aluminum nitrate, iron sulfate, ferric chloride, ferrous chloride/potassium manganate, ferrous sulfate/potassium manganate, ferrous chloride/potassium permanganate, ferrous sulfate/potassium permanganate one or more, one or more groups.
Preferably, the time of described solution boiling is 1min-1h.
Preferably, described solution boiling temperature is 110 �� 10 degree.
Preferably, described particles in solution size is between 20-75 nanometer.
Preferably, described constant voltage is 0.05-0.2MPa.
Modified ultrafilter membrane, cleaned, load granule can Reusability again.
Beneficial effect
1), the nano-particle Preferential adsorption pollutant of ultrafiltration membrane surface pre-deposition, reduce fouling membrane. Improve the service life of film, improve water treatment efficiency.
2), be physical absorption between nano-particle and the ultrafilter membrane of ultrafiltration membrane surface pre-deposition, after question response, wiped off with plastic wipers and wash can be completely removed with deionized water again, can Reusability.
3), the inventive method is simple to operation and is prone to scale use, is beneficial to popularization.
Accompanying drawing explanation
The scanning electron microscope diagram (SEM) of the 10mmol/L aluminum nanoparticles seethed with excitement 3 minutes through pre-deposition on poly (ether-sulfone) ultrafiltration membrane surface in Fig. 1, case study on implementation one.
In Fig. 2, case study on implementation one on poly (ether-sulfone) ultrafiltration membrane surface after the 10mmol/L aluminum nanoparticles that pre-deposition has seethed with excitement 3 minutes absorption flux decline figure to Organic substance bovine serum albumin (BSA) solution.
The scanning electron microscope diagram (SEM) of the 10mmol/L aluminum nanoparticles seethed with excitement 5 minutes through pre-deposition on poly (ether-sulfone) ultrafiltration membrane surface in Fig. 3, case study on implementation two.
In Fig. 4, case study on implementation two on poly (ether-sulfone) ultrafiltration membrane surface after the 10mmol/L aluminum nanoparticles that pre-deposition has seethed with excitement 5 minutes absorption flux decline figure to Organic substance sodium humate (HS) solution.
The scanning electron microscope diagram (SEM) of the 10mmol/L aluminum nanoparticles seethed with excitement 10 minutes through pre-deposition on poly (ether-sulfone) ultrafiltration membrane surface in Fig. 5, case study on implementation three.
In Fig. 6, case study on implementation three on poly (ether-sulfone) ultrafiltration membrane surface after the 10mmol/L aluminum nanoparticles that pre-deposition has seethed with excitement 10 minutes absorption flux decline figure to Organic substance sodium alginate (SA) solution.
In Fig. 7, case study on implementation four on polyvinylidene fluoride (PVDF) ultrafiltration membrane surface Scanning Electron microscope figure (SEM) through pre-deposition 0.5mmol/L iron nano-particle.
The repeatedly use of Organic substance bovine serum albumin (BSA) solution is adsorbed flux decline figure on polyvinylidene fluoride (PVDF) ultrafiltration membrane surface by Fig. 8, case study on implementation four after pre-deposition 0.5mmol/L iron nano-particle.
Detailed description of the invention
Below in conjunction with accompanying drawing and case study on implementation, the inventive method is described further. Should be understood that these cases are only limitted to illustrate the inventive method rather than the use scope of the restriction present invention.
Case study on implementation one
1), the sodium bicarbonate solution of 1 milliliter of 0.5mol/L is joined in 100 ml deionized water; then the Patent alum 10ml of 0.1mol/L is added; regulating pH with the sodium hydroxide solution of 0.1mol/L is 7 �� 0.1; by solution ebuillition of heated 3min; make the amorphous floc particle in solution, as it is shown in figure 1, solution left standstill 30min temperature is down to room temperature; when constant voltage 0.1MPa, by the particulate load in solution after boiling to poly (ether-sulfone) ultrafiltration membrane surface.
2), the sodium bicarbonate solution of 3 milliliters of 0.5mol/L is joined in 300 ml deionized water, it is subsequently adding bovine serum albumin (BSA) storing solution of the 3g/L of 1 milliliter, regulating pH with the hydrochloric acid solution of 0.1mol/L is 7 �� 0.1, by this BSA solution above-mentioned steps 1) in the pre-deposition poly (ether-sulfone) ultrafiltration membrane ultrafiltration of 10mmol/L aluminum nanoparticles, connecting data display equipment with electronic balance and gather data, the change of membrane flux is as shown in Figure 2. Greatly reduce the decay of membrane flux, after such as figure a period of time, still can keep the flux of about 75%.
Case study on implementation two
1), the sodium bicarbonate solution of 1 milliliter of 0.5mol/L is joined in 100 ml deionized water; then the Patent alum 10 milliliters of 0.1mol/L concentration is added; regulating pH with the sodium hydroxide solution of 0.1mol/L is 7 �� 0.1; by solution ebuillition of heated 5min; make the amorphous floc particle in solution, as it is shown on figure 3, by solution left standstill 30min to room temperature; when constant voltage 0.1MPa, by the particulate load in solution after boiling to poly (ether-sulfone) ultrafiltration membrane surface.
2), the sodium bicarbonate solution of 3 milliliters of 0.5mol/L is joined in 300 ml deionized water, it is subsequently adding the HS storing solution of the 3g/L of 1 milliliter, regulating pH with the hydrochloric acid solution of 0.1mol/L is 7 �� 0.1, by this HS solution above-mentioned steps 1) in the pre-deposition poly (ether-sulfone) ultrafiltration membrane ultrafiltration of 10mmol/L aluminum nanoparticles, connecting data display equipment with electronic balance and gather data, the change of membrane flux is as shown in Figure 4. The decay of membrane flux is substantially reduced, and still can keep the membrane flux excessively of 80% after such as scheming the filtration of time.
Case study on implementation three
1), the sodium bicarbonate solution of 1 milliliter of 0.5mol/L is joined in 100 ml deionized water; then the Patent alum 10 milliliters of 0.1mol/L is added; regulating pH with the sodium hydroxide solution of 0.1mol/L is 7 �� 0.1; by solution ebuillition of heated 10min; make the amorphous floc particle in solution, as it is shown in figure 5, by solution left standstill 30min to room temperature; when constant voltage 0.1MPa, by the particulate load in solution after boiling to poly (ether-sulfone) ultrafiltration membrane surface.
2), the sodium bicarbonate solution of 3 milliliters of 0.5mol/L is joined in 300 ml deionized water, it is subsequently adding the SA storing solution of the 3g/L of 1 milliliter, regulating pH with the hydrochloric acid solution of 0.1mol/L is 7 �� 0.1, by this SA solution above-mentioned steps 1) in the pre-deposition poly (ether-sulfone) ultrafiltration membrane ultrafiltration of 10mmol/L aluminum nanoparticles, connect data display equipment with electronic balance and gather data, the change of membrane flux as shown in Figure 6, still can keep the membrane flux excessively of 86% after such as scheming the filtration of time.
Case study on implementation four
1), the sodium bicarbonate solution of 1 milliliter of 0.5mol/L is joined in 100 ml deionized water, it is subsequently adding the liquor ferri trichloridi of the 0.1mol/L of 0.5ml, regulating pH with the sodium hydroxide solution of 0.1mol/L is 7 �� 0.1, under constant voltage 0.1MPa, by the particulate load in solution to polyvinylidene fluoride (PVDF) ultrafiltration membrane surface. Granule is as shown in Figure 7.
2) sodium bicarbonate solution of 3 milliliters of 0.5mol/L is joined in 300 ml deionized water, it is subsequently adding bovine serum albumin (BSA) storing solution of the 3g/L of 1 milliliter, regulating pH with the hydrochloric acid solution of 0.1mol/L is 7 �� 0.1, by the polyvinylidene fluoride (PVDF) ultrafiltration membrane ultrafiltration of 0.5mmol/L iron nano-particle with above-mentioned pre-deposition of this BSA solution, connecting data display equipment with electronic balance and gather data, the change of membrane flux is as shown in Figure 8. The ultrafilter membrane of load nano-particle can be reused repeatedly, here experiment three times are repeated, compared to first time, the membrane flux of second time and third time experiment recovers to reach 99.46% and 98.31%, it was shown that can be greatly reduced the irreversible membrane fouling of film after load nano-particle.
Claims (7)
1. the method that a nanoparticle coating is modified to ultrafilter membrane, it is characterised in that: specifically comprise the following steps that and A is joined in deionized water, then add flocculant; The mol ratio of the addition of A and flocculant is 20:1-1:2; After reacting completely, regulate pH by acid solution or alkaline solution and become neutrality; Then by solution ebuillition of heated, make the amorphous floc particle in solution, by solution left standstill to room temperature, under constant-pressure conditions, by the particulate load in solution to ultrafiltration membrane surface, obtain modified ultrafilter membrane;
Described A includes: one or more in sodium bicarbonate, potassium bicarbonate, dibastic sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate.
2. the method that a kind of nanoparticle coating as claimed in claim 1 is modified to ultrafilter membrane, it is characterised in that: described flocculant be in aluminum sulfate, aluminum chloride, aluminum nitrate, iron sulfate, ferric chloride, ferrous chloride/potassium manganate, ferrous sulfate/potassium manganate, ferrous chloride/potassium permanganate, ferrous sulfate/potassium permanganate one or more, one or more groups.
3. the method that a kind of nanoparticle coating as claimed in claim 1 or 2 is modified to ultrafilter membrane, it is characterised in that: the time of described solution boiling is 1min-1h.
4. the method that a kind of nanoparticle coating as claimed in claim 1 is modified to ultrafilter membrane, it is characterised in that: described solution boiling temperature is 110 �� 10 degree.
5. the method that a kind of nanoparticle coating as claimed in claim 1 is modified to ultrafilter membrane, it is characterised in that: described particles in solution size is between 20-75 nanometer.
6. the method that a kind of nanoparticle coating as claimed in claim 1 is modified to ultrafilter membrane, it is characterised in that: described constant voltage is 0.05-0.2MPa.
7. the method that a kind of nanoparticle coating as claimed in claim 1 is modified to ultrafilter membrane, it is characterised in that: described modified ultrafilter membrane, cleaned, load granule can Reusability again.
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| CN201510971390.1A CN105617870A (en) | 2015-12-22 | 2015-12-22 | Method for modifying ultrafiltration membrane through nano-particle coating |
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| CN201510971390.1A CN105617870A (en) | 2015-12-22 | 2015-12-22 | Method for modifying ultrafiltration membrane through nano-particle coating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055869A (en) * | 2017-04-25 | 2017-08-18 | 河海大学 | Microparticle for handling polluted-water is adsorbed and deep-bed filtration coupling device and method |
| CN108704487A (en) * | 2018-05-25 | 2018-10-26 | 哈尔滨工业大学 | A kind of filter membrane method of modifying based on metal oxide particle |
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| CN103406031A (en) * | 2013-07-29 | 2013-11-27 | 江苏大学 | Low-resistance high-flux soiling resistant type water treatment membrane and preparation method thereof |
| CN104230056A (en) * | 2014-09-21 | 2014-12-24 | 北京工业大学 | Method for relieving pollution to ultrafiltration membrane under joint action of pre-oxidation and membrane modification |
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2015
- 2015-12-22 CN CN201510971390.1A patent/CN105617870A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103406031A (en) * | 2013-07-29 | 2013-11-27 | 江苏大学 | Low-resistance high-flux soiling resistant type water treatment membrane and preparation method thereof |
| CN104230056A (en) * | 2014-09-21 | 2014-12-24 | 北京工业大学 | Method for relieving pollution to ultrafiltration membrane under joint action of pre-oxidation and membrane modification |
Non-Patent Citations (3)
| Title |
|---|
| JAESHIN KIM ET AL: "Effects of adsorbents on membrane fouling by natural organic matter", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| ZHENXIAO CAI ET AL: "Fouling mechanisms in low-pressure membrane filtration in the presence of an adsorbent cake layer", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| ZHENXIAO CAI ET AL: "NOM Removal by Adsorption and Membrane Filtration Using Heated Aluminum Oxide Particles", 《ENVIRON.SCI.TECHNOL.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055869A (en) * | 2017-04-25 | 2017-08-18 | 河海大学 | Microparticle for handling polluted-water is adsorbed and deep-bed filtration coupling device and method |
| CN107055869B (en) * | 2017-04-25 | 2022-11-25 | 河海大学 | Micro-particle adsorption and deep bed filtration coupling device and method for treating polluted water body |
| CN108704487A (en) * | 2018-05-25 | 2018-10-26 | 哈尔滨工业大学 | A kind of filter membrane method of modifying based on metal oxide particle |
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Application publication date: 20160601 |