CN107915270A - The method of comprehensive utilization of magnetic polymer material after one kind absorption Cr (VI) - Google Patents
The method of comprehensive utilization of magnetic polymer material after one kind absorption Cr (VI) Download PDFInfo
- Publication number
- CN107915270A CN107915270A CN201711030796.5A CN201711030796A CN107915270A CN 107915270 A CN107915270 A CN 107915270A CN 201711030796 A CN201711030796 A CN 201711030796A CN 107915270 A CN107915270 A CN 107915270A
- Authority
- CN
- China
- Prior art keywords
- absorption
- polymer material
- magnetic polymer
- magnetic
- comprehensive utilization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention disclose a kind of method of comprehensive utilization for adsorbing the magnetic polymer material after Cr (VI), first, first the magnetic polymer material after absorption Cr (VI) is collected, is uniformly mixed, cleaning or microwave assistant cleaning, Magneto separate post activation are assisted using ultrasound；Then sampling is characterized, and finally uses it for heavy metal, methylene blue pigment and chlorophenols environmental contaminants in absorption and degrading waste water.The present invention is collected using ultrasonic assistance Magneto separate vacuum drying Synergistic method and the magnetic polymer material NMP Cr after adsorbing Cr (VI) are recycled in activation；This method has the advantages that good dispersion, technique are simple, organic efficiency is high, it can be easy to the drawbacks such as reunion, bad dispersibility to avoid magnetic composite in removal process, the pattern for not only contributing to preserve magnetic composite also saves process and cost, waste material containing chromium can also be avoided to flow into environmental system, pollute environment.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of the magnetic polymer material after absorption Cr (VI), Cr is specially adsorbed
(VI) method of comprehensive utilization of the magnetic polymer material as new adsorbent and catalyst after.The present invention will absorption Cr (VI)
Rear magnetic polymer material is collected, after characterization activation, can efficiently, metallic copper, nickel, cadmium in high-selectivity adsorption and degrading waste water
Deng environmental contaminants such as heavy metal, methylene blue pigment and chlorophenols.
Background technology
With further speeding up for global industry process, the industry such as steel, plating, process hides and paint pigment chemistry obtains
Significant progress.In the development of these industries, the effect of heavy metal can not be ignored, but at the same time, thing followed weight
Environmental pollution caused by metal also result in the extensive concern of people.For example, chromium is in aqueous with Cr (VI) and Cr (III)
Two kinds of valence states exist, and Cr (VI) has good water solubility, strong oxidizing property, and toxicity is 100 times of Cr (III), is the United Nations's ring
The typical environment persistent pollutant that border administration (U.S. EPA) announces.How it is carried out effectively removing and recycling is not only environment
The research hotspot in protection field, and the focus of attention of resource regeneration.Functional magnetic composite material because its preparation method is various,
Technique relatively easily controls, have the function of structure, predictability, Modulatory character and tailorability and be increasingly domestic surgery
The research hotspot of family, and have a wide range of applications in fields such as material, chemistry, medicine, biology and environmental projects.Due to it
With magnetism, it can be conveniently separated and recycle using magnetic separation technique, be successfully applied to the research of Wastewater processing absorbent.Shen
Please person be also successfully prepared amino functional Fe3O4 polymer composites and be used successfully to the absorption of Cr in water (VI)
With removing (chemical journal, 2009,67 (13), 1509-1514；J.Mater.Sci.2010,45,5291–5301；
J.Hazard.Mater.2010,182, 295–302；Ind.Eng.Chem.Res.2013,52,12723-12732 etc.).
Although they have Cr (VI) very high removal efficiency, highest adsorbance adsorbs Cr (VI) up to 370mg/g
Material afterwards is if its collecting and processing can similarly not become a kind of new environmental pollution solid waste.For this reason, applicant was once
The organic synthesis aspect for being used for the selective oxidation of alcohol as catalyst was attempted, and achieves pre-test achievement (China
B volumes of science:Chemistry, 2010,40 (11), 1575-1583).However, since the waste material component after processing Cr (VI) is very multiple
It is miscellaneous, as waste material component is：Different amino, different macromolecule ratios, different magnetic core contents, difference Cr (VI) adsorbance, different suctions
The material of sub conditione (such as temperature, pH value) etc. mixes the waste material of composition；The component of its waste material is unknown, and structure is unknown,
Therefore the comprehensive utilization of its system is not yet effectively carried out.
The content of the invention
The present invention is directed to the above-mentioned deficiency of the prior art, there is provided one kind is easy to operate, efficient, effectively can recycle and integrate
Utilize the method for comprehensive utilization for adsorbing the magnetic polymer material after Cr (VI).
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：Magnetism after one kind absorption Cr (VI) is high
The method of comprehensive utilization of molecular material, will adsorb after the magnetic polymer material after Cr (VI) is collected and be activated, characterized and comprehensive
Close and utilize, this method includes：First, first the magnetic polymer material after absorption Cr (VI) is collected, be uniformly mixed, used
Ultrasound assists cleaning or microwave assistant cleaning, Magneto separate post activation；Then sampling is characterized, and is finally used it for adsorbing and is dropped
Solve heavy metal in waste water, methylene blue pigment and chlorophenols environmental contaminants.
Metal heavy metal of the present invention is copper, nickel, cadmium；It is on phenol (hydroxy benzenes) phenyl ring that the chlorophenols, which is,
A kind of organic compound that hydrogen atom is substituted and formed by one or more chlorine atoms, including from mono-substituted monochlorphenol to taking entirely
19 kinds of isomers including the pentachlorophenol in generation.
The method of comprehensive utilization of magnetic polymer material after the above-mentioned absorption Cr (VI) of the present invention, wherein after absorption Cr (VI)
Magnetic polymer material collection and activation, specific preparation process includes：By the magnetic after the absorption Cr (VI) of separate sources
Property high molecular material be collected, then mix that (mixing herein is by the magnetic high score after separate sources, absorption Cr (VI)
Sub- material is mixed, because material source can be relatively more, for example under different batches, condition of different pH, different temperatures, no
With Cr (VI) material of concentration, the structure and compositions of these materials can some difference)；Assisted in ultrasound or microwave assistant acts on
Lower washing, then Magneto separate, activate up to activate after salvage material (NMP-Cr).
Deionized water is respectively adopted for the above-mentioned washing of the present invention and ethanol respectively washs 2-5 times.
The above-mentioned Magneto separate of the present invention is for non-magnetic constituents caused by removing washing, in addition uses Magneto separate can be with
Effectively collect salvage material.
The above-mentioned activation of the present invention be using 40~80 DEG C of vacuum drying 4~24 it is small when, up to the salvage material after activating
(NMP-Cr)；The purpose of activation is to improve the specific surface area and dispersiveness of material, so as to effectively improve adsorption efficiency and adsorbance；
Preferable activation temperature is 50-70 DEG C, when the time is 10~15 small.
Magnetic polymer material, its magnetic core after the above-mentioned absorption Cr (VI) of the present invention are ferroso-ferric oxide, macromolecule layer without
It is strict with, the form of the Cr (VI) of absorption is without strict demand.
The ultrasonic power that above-mentioned steps ultrasound of the present invention is assisted is 20-40kHz, is preferably 25-35kHz；The microwave
The microwave power of assistance is 300M-300G Hz, is preferably 1000M-200GHz.
The method of comprehensive utilization of magnetic polymer material after the above-mentioned absorption Cr (VI) of the present invention, wherein after absorption Cr (VI)
Magnetic polymer material characterization, specifically include：By the salvage material (NMP-Cr) after activation, solid sample passes through infrared light
Spectrum, vibrating specimen magnetometer, x-ray photoelectron spectroscopy measure its composition, magnetic and structure；By by sample with 1:1 (volume
Than) after nitric acid resolution, with aas determination wherein iron content, to calculate the content of wherein magnetic core；With 1%NaOH
Cr (VI) in methanol solution desorption material, and it is solid using Cr (VI) in diphenylcarbazide (DPCI) spectrophotometry material
Carrying capacity.The main purpose of the step is to measure the performance of salvage material, especially pattern, Cr (VI) content, so as to be follow-up
Comprehensive utilization lays the first stone.
The method of comprehensive utilization of magnetic polymer material after the above-mentioned absorption Cr (VI) of the present invention, wherein after absorption Cr (VI)
Magnetic polymer material comprehensive utilization：The salvage material (NMP-Cr) after activation is weighed in containing heavy metal or pigment or chlorine
In the aqueous solution of phenol pollutant so that NMP-Cr's feeds intake as 0.1-100mg/L；Solution ph is adjusted to 2-9, isothermal vibration
Afterwards, hydrogen peroxide is added so that substance withdrawl syndrome of the hydrogen peroxide in system be 0.2-80mmol/L, after Magneto separate, is detected molten
The residual concentration of pollutant in liquid, investigates absorption and degradation effect；Above-mentioned comprehensive utilization, some is for pollutant
Degraded, such as Hg (II) and chlorophenols, some is the absorption for being directly used in heavy metal, such as Cu (II), Ni
(II), the heavy metal such as Cd (II).
The preferably 0.4-20mg/L that feeds intake of the above-mentioned NMP-Cr of the present invention, solution ph is preferably 3-6, and hydrogen peroxide is in system
In substance withdrawl syndrome be preferably 1-20mmol/L.
The advantages of the present invention：
1. the present invention is collected using ultrasonic assistance-Magneto separate-vacuum drying Synergistic method and activation recycling absorption Cr (VI)
Magnetic polymer material NMP-Cr afterwards；This method has the advantages that good dispersion, technique are simple, organic efficiency is high, can keep away
Exempt from magnetic composite in removal process and be easy to (the ultrasound assistance washing or micro- particularly therein of the drawbacks such as reunion, bad dispersibility
Ripple assists washing and vacuum drying effectively to overcome above-mentioned drawback), the pattern for not only contributing to preserve magnetic composite is also saved
Process and cost, can also avoid waste material containing chromium from flowing into environmental system, pollute environment.
2. the magnetic polymer material NMP-Cr after present invention absorption Cr (VI) can make full use of the Cr in salvage material
Coordination activity center, π-π interactions and the pollutants such as heavy metal of phenyl ring in macromolecule macromolecule layer realize high absorption
The adsorption such as Coordination Adsorption of amount, high selectivity；Further realize that the original position of pollutant is urged using the oxidation of Cr (VI)
Change degraded, while Cr (VI) is reduced to Cr (III)；Recycle H2O2, can also be successfully by Cr (III) oxygen again as oxidant
Cr (VI) is turned to, realizes recycling for NMP-Cr, it is possible to achieve turn waste into wealth.
3. the present invention first mixes the magnetic polymer material after the absorption Cr (VI) in various complicated sources, collect
Middle processing, and by mixing, washing and activation step, obtains that specific surface area is big and the NMP-Cr of good dispersion, can realize pair
The absorption and degraded of environmental contaminants, realize the purpose of comprehensive utilization.
3. present invention employs ultrasound assist washing activation salvage material, using the cavitation effect of ultrasonic wave, fuel factor and
Mechanical effect so that salvage material surface impurity can quickly ooze out, and effectively reduce detergent consumption and washing cost, improve
The dispersiveness of material；And electromagnetic field caused by microwave can accelerate salvage material surface impurity to be expanded from solid interior to solid liquid interface
Scattered speed, in washing process, under the action of microwave field, water or ethanol are changed into excitation state by high-speed rotation state, this is
A kind of unstable state of high-energy, discharges itself unnecessary energy and returns to ground state, the energy discharged will be passed to back
Material is received, is conducive to accelerate the warm-up movement of salvage material, improves the dispersiveness of material, while reduce washed surface impurity
The time of solid liquid interface is diffused to by solid interior, as a result improves rate of washing, reduces washing times and washing loss, and energy
Wash temperature is reduced, ensures the pattern of salvage material to greatest extent, it is ensured that material can be with high efficiente callback.
Brief description of the drawings
Fig. 1 be the present invention absorption Cr (VI) after magnetic polymer material NMP-Cr comprehensive utilization flow diagram；
Fig. 2 is according to embodiments of the present invention, the transmission of the magnetic polymer material NMP-Cr after obtained absorption Cr (VI)
Electromicroscopic photograph；
Fig. 3 is according to embodiments of the present invention, the magnetic hysteresis of the magnetic polymer material NMP-Cr after obtained absorption Cr (VI)
Loop line；
Fig. 4 is according to embodiments of the present invention, and the X- of the magnetic polymer material NMP-Cr after obtained absorption Cr (VI) is penetrated
Ray diffraction diagram；
Fig. 5 is according to embodiments of the present invention, the weightlessness of the magnetic polymer material NMP-Cr after obtained absorption Cr (VI)
Curve；
Fig. 6 is according to embodiments of the present invention, and magnetic polymer material NMP-Cr's after obtained absorption Cr (VI) is infrared
Spectrogram.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described further present disclosure, makes the purpose of the present invention and effect
Fruit is confirmed, but the present invention is not limited solely to following embodiments.
Embodiment
The synthesis of amino functional nanometer Fe_3O_4 magnetic high-molecular composite material and characterization (serial 1-5, series 6 is similar,
MMA is changed to St) (chemical journal, 2009,67 (13), 1509-1514；J.Mater.Sci.2010,45,5291–5301；
J.Hazard. Mater.2010,182,295–302；Ind.Eng.Chem.Res.2013,52,12723-12732 etc.) have in
Portion of material synthesizes the record with characterization：
1 nanometer Fe3O4The synthesis of particle
Using Co deposited synthesis nanometer Fe3O4Particle, according to Fe2+:Fe3+=1.5:2 (the ratio between amounts of material), which are prepared, to be contained
There is Fe2+And Fe3+After the solution of ion, fully dissolving, alkalescence is provided using ammonium hydroxide, adjusts its pH value to 8~9, mixing speed is
500 r·min-1, reaction temperature 353K, reaction time 1h.Shown in reaction principle such as reaction equation (1)：
Fe2++2Fe3++8OH-→Fe3O4+4H2O (1)
After the completion of reaction, Magneto separate, it is~7.0 to be washed with deionized to pH value, and is washed with ethanol, and 333K vacuum is done
Dry 12h, it is spare.
2 Coated with Oleic Acid nanometer Fes3O4Particle
By the nanometer Fe of 1.0g3O4Particle is dispersed in 200mL ethanol solutions, under conditions of reaction temperature is 353K, is stirred
It is 500rmin- to mix speed1, 5mL oleic acid is at the uniform velocity added dropwise in 20min.After being added dropwise to complete, the reaction was continued 1h.Reaction is completed
Afterwards, Magneto separate, it is~7.0 to be washed with deionized to pH value, and is washed with ethanol, and 333K is dried in vacuo 12h, spare.
3 Epoxy functionalized polymeric PTC materials nanometer Fes3O4The synthesis of magnetic material
2.0g PVA217 are dissolved in 200mL deionized waters, in this, as dispersant；By the Fe of Coated with Oleic Acid3O4
Grain is added in PVA solution, and ultrasonic disperse 1min, by a certain amount of monomer MMA, DVB, GMA are dissolved in 5mL ethanol respectively,
It is added drop-wise to successively in reaction system under agitation, ultrasonic disperse 2min, makes reaction system be uniformly dispersed.1.0g BPO (are triggered
Agent) it is dissolved in 20mL hot ethanol solution, it is added drop-wise under agitation in reaction system.In 353K, 700rmin-1Rotating speed
Under, 3h is reacted, Magneto separate, is washed each 3 times with deionized water and ethanol, and 333K is dried in vacuo 12h, spare.
4 nanometer Fes3O4The surface amino groups modification of magnetic polymer material
Under conditions of 353K, condensing reflux, 25mL methanol adds 1.25g nanometer Fes as solvent3O4Magnetic high-molecular
Composite material, ultrasonic disperse 1min, a certain amount of amine is added drop-wise in reaction system under agitation, mixing speed 300r
min-1, react 8h.After the completion of reaction, Magneto separate, it is~7.0 to be washed with deionized to pH value, and is washed with methanol, 333K
12h is dried in vacuo, it is spare.
Consider amino functional nanometer Fe3O4The influence of various factors in magnetic high-molecular composite material building-up process,
By varying amino functional nanometer Fe3O4Organic functional groups ethylenediamine (EDA) in magnetic high-molecular composite material building-up process
Dosage, the dosage of functional group glycidyl methacrylate (GMA), the dosage of crosslinking agent divinylbenzene (DVB), amine
Species and the content of nanometer Fe_3O_4 magnetic core be prepared for five series totally 22 kinds of amino functional nanometer Fe_3O_4 magnetic high-moleculars
Composite material (table 1-5), and 6 kinds of materials (table 6) of styrene (St) series；Its specific synthetic schemes is listed in the table below respectively.Ammonia
Base functionalized nano Fe3O4 magnetic high-molecular composite material building-up processes are as shown in formula：
Different monomers (glycidyl methacrylate (GMA), methyl methacrylate (MMA), styrene (St)), hand over
Join agent (DVB) and dosage, different amino (ethylenediamine (EDA), diethylenetriamine (DETA), triethylene tetramine (TETA), four ethene
Five amine (TEPA)) and the material of dosage and different magnetic core contents.
Table 1：The amino functional nanometer Fe of Organic functional groups ethylenediamine (EDA) different amounts3O4Magnetic high-molecular is compound
The preparation of material
*1Note：2mL DVB(0.0143mol)；4mL MMA(0.0400mol)；2mL GMA(0.0133mol)；
*2Note：1st, 2,5,10,15,20,25 the ratio between amount of material of EDA and GMA dosages is represented
Table 2：The amino functional nanometer Fe of function monomer (GMA) different amounts3O4The preparation of magnetic high-molecular composite material
*Note：Fixed GMA：EDA=1：15(molar ratio)
Table 3：The amino functional nanometer Fe of crosslinking agent (DVB) different amounts3O4The preparation of magnetic high-molecular composite material
Table 4：The amino functional nanometer Fe of variety classes amine3O4The preparation of magnetic high-molecular composite material
Table 5：The amino functional nanometer Fe of magnetic core different amounts3O4The preparation of magnetic high-molecular composite material
Table 6：The amino functional polymer composite of comonomer (St) different amounts synthesis
*1Note：0.5mL DVB(0.0035mol)；4mL St(0.0348mol)；8mL GMA(0.0133mol)；
*2Note：St- (0.5-x-8) refers to DVB, the copolymer of St, GMA, and the dosage of three kinds of monomers is respectively 0.5, x,
8mL, x are the dosage of monomer St；EDA-NMPs refers to the amino functional composite material for functional group with ethylenediamine (EDA).
The synthetic route of amino functional magnetic high-molecular composite material：
After amino functional magnetic high-molecular composite material absorption Cr (VI) of above-mentioned preparation, method using the present invention into
Row comprehensive utilization：
(1) magnetic polymer material after absorption Cr (VI) is collected, after mixing, is respectively assisted with deionized water and ethanol in ultrasound
(ultrasonic power 30kHz) under effect is helped to wash 3 times, (Magneto separate is this area conventional method to Magneto separate, no longer superfluous herein
State) after, when 60 DEG C of vacuum drying 12 are small, up to the salvage material (NMP-Cr) after activation；
Or
The magnetic polymer material after absorption Cr (VI) is collected, after mixing, with deionized water and ethanol respectively in microwave assistant
(microwave wave power is 3000MHz) washs 3 times under effect, after Magneto separate, when 60 DEG C of vacuum drying 12 are small, up to returning after activation
Receive material (NMP-Cr).
(2) characterization of the magnetic polymer material after Cr (VI) is adsorbed：Fig. 2 is the transmission electron microscope photo of NMP-Cr.Understand,
The average grain diameter of NMP-Cr is about 10nm；The nanoscale of material makes the increase of its specific surface area, is conducive to absorption and degradation reaction
Quick progress.Fig. 3 is the x-ray diffraction pattern of NMP-Cr.As can be seen that there is Fe3O46 typical, 2 θ angles are located at
The diffraction maximum of 30.1 ° (220), 35.5 ° (311), 43.1 ° (400), 53.4 ° (422), 57.0 ° (511) and 62.6 ° (440).Can
See that the crystalline phase of NMP-Cr does not change, maintain Fe3O4Spinel structure.The purer Fe of the diffraction maximum of NMP-Cr3O4
There is wider peak width to show it with less scale.Fig. 4 is the weight-loss curve of NMP-Cr；Understand, the differential of pyrolysis weight loss is bent
Line (DTG) nearby has three obvious weightless peaks at~92 DEG C ,~399 DEG C and~886 DEG C, wherein, the weightlessness near~90 DEG C
It can be attributed to the weightlessness of free water；Nearby there is obvious broadening weightless peak at~399 DEG C, after this explanation absorption Cr (VI) due to
The structure of material changes, and has delayed the decomposition of copolymerized macromolecule layer；And the peaks of the appearance nearby at~886 DEG C, it can belong to
To be attached on NMP-Cr the pyrolysis weight loss of " Cr (VI)-N " unit by coordination.Fig. 5 is the hysteresis curve of NMP-Cr
Curve；Understand that its intensity of magnetization is 9.82emu/g.Illustrate that NMP-Cr magnetic responses are good, good point can be realized under magnetic field
From.Fig. 6 is the infrared spectrogram of NMP-Cr.Understand, 3400cm-1It can be attributed to-OH ,-NH2Stretching vibration absworption peak；2925,
2850cm-1It can be attributed to-CH2- ,-CH3Stretching vibration absworption peak；1725cm-1For the stretching vibration absworption peak of C=O；
1575cm-1It can be attributed to-NH2With the stretching vibration absworption peak of-NH-, red shift is to~1636cm after the load C r (VI)-1, and
In~942cm-1,~780cm-1,~518cm-1Nearby there are three peaks, be attributed to the absworption peak of Cr-O and Cr-N keys.
Weigh salvage material (NMP-Cr) 0.05g by by sample with 1:After the resolution of 1 (volume ratio) nitric acid, Atomic absorption is used
Spectrographic determination wherein iron content, to calculate wherein magnetic core (Fe3O4) content:For 19.24%.Taken off with 1%NaOH methanol solutions
Cr (VI) in enclosure material, and Cr (VI) supported quantities are used in diphenylcarbazide (DPCI) spectrophotometry material as 200
mg/g。
Above-mentioned characterization illustrates that operating procedure of the present invention is simple, of low cost, the NMP-Cr even particle size distributions recycled,
Property is stablized.
(3) comprehensive utilization of Cr (VI) magnetic polymer material afterwards is adsorbed：
Absorption and recycling of the gained NMP-Cr applied to the Cu (II) in waste water will be activated.A series of 25.00mL 10 are taken,
100,500mg/L Cu (II) solution, is separately added into 0.02g NMP-Cr, and constant temperature shakes under adsorption temp 308K, 150r/min
Swing, adsorption time 3h, pH value range 2.0~10.0, measure absorption Optimal pH；Take Cu (II) solution of 0~1000mg/L
25mL, is separately added into 0.02g NMP-Cr, and adsorption temp is respectively 308K, and adsorption time 3h, measures its saturated extent of adsorption.
Cu (II) solution 25mL of 100mg/L is taken, is separately added into 0.02g NMP-Cr, adsorption temp is respectively 303K, 308K, 313
K, 1~180min of adsorption time, studies its dynamics and macroscopic property.Using Cu (II) in solution after AAS measure absorption
Residual concentration.The result shows that gained NMP-Cr has higher absorption property, optimal pH 4.0, absorption isotherm to Cu (II)
Substantially conform to Langmuir patterns, saturated extent of adsorption 320mg/g, is 3.1~397 times of document report.Adsorption dynamics adsorption kinetics is ground
Study carefully and show, adsorption process can reach balance in 5min, meet pseudo-second order kinetic model.
Absorption and recycling of the gained NMP-Cr applied to the Ni (II) in waste water will be activated.A series of 25.00mL 10 are taken,
100,500mg/L Ni (II) solution, is separately added into 0.02g NMP-Cr, and constant temperature shakes under adsorption temp 308K, 150r/min
Swing, adsorption time 3h, pH value range 2.0~10.0, measure absorption Optimal pH；Take Ni (II) solution of 0~1000mg/L
25mL, is separately added into 0.02g NMP-Cr, and adsorption temp is respectively 308K, and adsorption time 3h, measures its saturated extent of adsorption.
Ni (II) solution 25mL of 100mg/L is taken, is separately added into 0.02g NMP-Cr, adsorption temp is respectively 303K, 308K, 313
K, 1~180min of adsorption time, studies its dynamics and macroscopic property.Using Ni (II) in solution after AAS measure absorption
Residual concentration.The result shows that gained NMP-Cr has higher absorption property, optimal pH 4.0, absorption isotherm to Ni (II)
Substantially conform to Langmuir patterns, saturated extent of adsorption 320mg/g, is 1.5~200 times of document report.Adsorption dynamics adsorption kinetics is ground
Study carefully and show, adsorption process can reach balance in 5min, meet pseudo-second order kinetic model.
Activation gained NMP-Cr is applied to pentachlorophenol catalytic degradation in water.A series of 25.00mL concentration are taken to be respectively
The pentachlorophenol solution of 0.5-200mg/L, it is 3.0-9.0 to adjust solution ph, is separately added into the NMP-Cr of the 0.02g present invention,
30% H2O21-100 μ L, 35 DEG C, 150r/min shaking tables vibrate；Sampled every 1min, 1 drop is added in samples taken
10%Na2SO3Stopped reaction；In order to exclude to be due to factor that suction-operated reduces pentachlorophenol residual concentration in the solution,
With the NMP-Cr after the desorption degraded of 1%NaOH methanol solutions；Measured respectively using liquid chromatogram after being catalyzed in solution and desorption liquid
Pentachlorophenol residual concentration Ce.Calculate degradation rate.It was found that in the range of pH value 3.0-4.5, NMP-Cr/H2O2System exists
Nearly 100% degraded pentachlorophenol in 5min.The dosage of NMP-Cr is 0.8-4.0g/L, H2O2Concentration be 4.08mmol/L, pentachlorophenol
Concentration<During 20mg/L, pentachloro- Phenol degradation rate can be up to more than 99%.Degradeds of the NMP-Cr after 5 times recycle to pentachlorophenol
Rate remains to keep more than 95%, is the catalyst of function admirable.
Activation gained NMP-Cr is applied to Hg (II) absorption and ira situ degradation in water.Take a series of 25.00mL concentration point
Not Wei 10-500mg/L Hg (II) solution, adjust solution ph be 2.0~10.0, be separately added into 0.05g the present invention
NMP-Cr, oscillation rate are 150 revs/min, and the time is 30 minutes；The Hg (II) of solution after being adsorbed using Atomic Fluorescence Spectrometry
Residual concentration Ce, calculate adsorbance.It was found that in the range of pH value 4.0-6.0, NMP-Cr is to the adsorption rate of Hg (II) up to closely
100%；Magneto separate after absorption, the magnetic composite for having adsorbed Hg (II) is distributed in 10mL acetonitriles, adds 30% H2O2
40uL, oscillation rate are 150 revs/min, and Hg (II) degradation rate can realize nearly 100%.NMP-Cr is after 10 times recycle to Hg
(II) absorption remains to keep more than 95% with degradation rate, is absorption and the degradable material of function admirable.
Absorption and recycling of the gained NMP-Cr applied to the Cd (II) in waste water will be activated.A series of 25.00mL 10 are taken,
Cd (II) solution of 100,500 mg/L, is separately added into 0.02g NMP-Cr, and constant temperature shakes under adsorption temp 308K, 150r/min
Swing, adsorption time 3h, pH value range 2.0~10.0, measure absorption Optimal pH；Take Cd (II) solution of 0~500mg/L
25mL, is separately added into 0.02g NMP-Cr, and adsorption temp is respectively 308K, and adsorption time 3h, measures its saturated extent of adsorption.Take
Cd (II) solution 25mL of 100 mg/L, is separately added into 0.02g NMP-Cr, and adsorption temp is respectively 303K, 308K, 313K, is inhaled
Attached 1~180min of time, studies its dynamics and macroscopic property.Using the residue of Cd (II) in solution after AAS measure absorption
Concentration.The result shows that gained NMP-Cr has higher absorption property to Cd (II), optimal pH 6.0, absorption isotherm is basic
Meet Langmuir patterns, saturated extent of adsorption 258mg/g, is 1.8~228 times of document report.Adsorption dynamics adsorption kinetics research table
Bright, adsorption process can reach balance in 10min, meet pseudo-second order kinetic model.
Absorption and ira situ degradation of the gained NMP-Cr applied to water methylene cyanine will be activated.Take a series of
25.00mL concentration is respectively the methylene blue solution of 10-1000mg/L, and it is 2.0~10.0 to adjust solution ph, is separately added into
The NMP-Cr of the 0.05g present invention, oscillation rate are 150 revs/min, and the time is 30 minutes；Solution after being adsorbed using ultraviolet spectrometer
Methylene blue residual concentration Ce, calculate adsorbance.It was found that in the range of pH value 4.0-8.0, NMP-Cr is to methylene blue
Adsorption rate reaches nearly 100%；Magneto separate after absorption, the NMP-Cr for having adsorbed methylene blue is distributed in 10mL acetonitriles, is added
30% H2O240uL, oscillation rate are 150 revs/min, and the degradation rate of methylene blue can realize nearly 100%.NMP-Cr is through 10 times
Absorption after recycling to methylene blue remains to keep more than 95% with degradation rate, is absorption and the degraded material of function admirable
Material.
A kind of method of comprehensive utilization of absorption Cr (VI) of the present invention magnetic polymer material afterwards, is experimentally confirmed：
The inventive method is simple, of low cost, the magnetic high-molecular after the absorption Cr (VI) recycled after collecting, characterizing and activate
There is material even particle size distribution, property to stablize；What is more important its can efficiently, gold in high-selectivity adsorption and degrading waste water
Belong to the environmental contaminants such as heavy metal, methylene blue pigment and the chlorophenols such as copper, nickel, cadmium；Start using the absorption for being waste material
The beginning of Cr (VI) material recovery deep exploitations again of magnetic polymer material afterwards.
The present invention is equally applicable except the pentachlorophenol in above-mentioned example or 2,4,6- trichlorophenols, other chlorophenols；
Specific such as following table (table 7) is shown：
The physicochemical properties of 7 chlorophenols of table
*NR：Do not report
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, to any modifications and changes of the invention made, protection scope of the present invention is both fallen within.
Claims (10)
1. the method for comprehensive utilization of the magnetic polymer material after one kind absorption Cr (VI), it is characterised in that：Will absorption Cr (VI)
Magnetic polymer material afterwards is activated, characterized and comprehensively utilized after collecting：First, the magnetism that will first adsorb after Cr (VI) is high
Molecular material is collected, is uniformly mixed, and cleaning or microwave assistant cleaning, Magneto separate post activation are assisted using ultrasound；Then take
Sample is characterized, and finally uses it for heavy metal, methylene blue pigment and chlorophenols environmental contaminants in absorption and degrading waste water.
2. the method for comprehensive utilization of the magnetic polymer material after absorption Cr (VI) according to claim 1, its feature exist
In：The metal heavy metal is copper, nickel, cadmium；It is that hydrogen atom on phenol phenyl ring is one or more that the chlorophenols, which is,
A kind of organic compound that chlorine atom substitutes and formed, 19 including from mono-substituted monochlorphenol to the pentachlorophenol substituted entirely
Kind isomers.
3. the method for comprehensive utilization of the magnetic polymer material after absorption Cr (VI) according to claim 1, its feature exist
In：The collection and activation of the magnetic polymer material after Cr (VI) are wherein adsorbed, specific preparation process includes：By separate sources
Absorption Cr (VI) after magnetic polymer material be collected, then mix；Washed in the case where ultrasound is assisted or microwave assistant acts on
Wash, then Magneto separate, activate up to activate after salvage material.
4. the method for comprehensive utilization of the magnetic polymer material after the absorption Cr (VI) stated according to claim 3, it is characterised in that：
Deionized water is respectively adopted in the washing and ethanol respectively washs 2-5 times.
5. the method for comprehensive utilization of the magnetic polymer material after the absorption Cr (VI) stated according to claim 3, it is characterised in that：
The activation be using 40~80 DEG C vacuum drying 4~24 it is small when；Preferable temperature is 50-70 DEG C, and the time is small for 10~15
When.
6. the method for comprehensive utilization of the magnetic polymer material after the absorption Cr (VI) stated according to claim 3, it is characterised in that：
Magnetic polymer material, its magnetic core after the absorption Cr (VI) are ferroso-ferric oxide.
7. the method for comprehensive utilization of the magnetic polymer material after the absorption Cr (VI) stated according to claim 3, it is characterised in that：
The ultrasonic power that the ultrasound is assisted is 20-40kHz；Preferably 25-35kHz；The microwave power of the microwave assistant is
300M-300G Hz；Preferably 1000M-200GHz.
8. the method for comprehensive utilization of the magnetic polymer material after the absorption Cr (VI) stated according to claim 1, it is characterised in that：
The characterization of Cr (VI) magnetic polymer material afterwards is adsorbed, is specifically included：By the salvage material after activation, solid sample passes through infrared
Spectrum, vibrating specimen magnetometer, x-ray photoelectron spectroscopy measure its composition, magnetic and structure；By by sample with 1:1 nitric acid
After resolution, with aas determination wherein iron content, to calculate the content of wherein magnetic core；With 1%NaOH methanol solutions
Cr (VI) in desorption material, and using Cr (VI) supported quantity in diphenylcarbazide (DPCI) spectrophotometry material.
9. the method for comprehensive utilization of the magnetic polymer material after the absorption Cr (VI) stated according to claim 1, it is characterised in that：
Adsorb the comprehensive utilization of Cr (VI) magnetic polymer material afterwards：Weigh the salvage material after activation in containing heavy metal or pigment or
In the aqueous solution of chlorophenol pollutants so that salvage material after activation feeds intake as 0.1-100mg/L；Solution ph is adjusted to 2-
9, after isothermal vibration, add hydrogen peroxide so that substance withdrawl syndrome of the hydrogen peroxide in system is 0.2-80mmol/L, Magneto separate
Afterwards, the residual concentration of pollutant in solution is detected, investigates absorption and degradation effect.
10. the method for comprehensive utilization of the magnetic polymer material after the absorption Cr (VI) stated according to claim 9, its feature exist
In：Salvage material after the activation feeds intake as 0.4-20mg/L；Solution ph is 3-6, material of the hydrogen peroxide in system
Amount concentration be 1-20mmol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711030796.5A CN107915270A (en) | 2017-10-30 | 2017-10-30 | The method of comprehensive utilization of magnetic polymer material after one kind absorption Cr (VI) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711030796.5A CN107915270A (en) | 2017-10-30 | 2017-10-30 | The method of comprehensive utilization of magnetic polymer material after one kind absorption Cr (VI) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107915270A true CN107915270A (en) | 2018-04-17 |
Family
ID=61894938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711030796.5A Pending CN107915270A (en) | 2017-10-30 | 2017-10-30 | The method of comprehensive utilization of magnetic polymer material after one kind absorption Cr (VI) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107915270A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554367A (en) * | 2018-05-22 | 2018-09-21 | 华东理工大学 | A method of preparing magnetic Nano iron oxide particle adsorbent |
| CN110975823A (en) * | 2019-12-23 | 2020-04-10 | 徐州工程学院 | Method for desorbing soybean hull heavy metal ion adsorbent |
| CN113385147A (en) * | 2021-07-19 | 2021-09-14 | 西北大学 | Application of composite adsorption material in simultaneous removal of phenol and Cr (VI) in wastewater and method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623782A (en) * | 2012-08-21 | 2014-03-12 | 北京有色金属研究总院 | Preparation method for composite magnetic adsorption material and method for removing heavy metal ions in waste water |
| CN105642222A (en) * | 2016-02-29 | 2016-06-08 | 衡阳师范学院 | Preparation method and application of magnetic recyclable adsorbent |
-
2017
- 2017-10-30 CN CN201711030796.5A patent/CN107915270A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623782A (en) * | 2012-08-21 | 2014-03-12 | 北京有色金属研究总院 | Preparation method for composite magnetic adsorption material and method for removing heavy metal ions in waste water |
| CN105642222A (en) * | 2016-02-29 | 2016-06-08 | 衡阳师范学院 | Preparation method and application of magnetic recyclable adsorbent |
Non-Patent Citations (2)
| Title |
|---|
| 胡奇林 等: "《综合化学实验》", 28 February 2013, 宁夏人民教育出版社 * |
| 闫军锋: "《电子材料与器件实验教程》", 31 May 2016, 西安电子科技大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554367A (en) * | 2018-05-22 | 2018-09-21 | 华东理工大学 | A method of preparing magnetic Nano iron oxide particle adsorbent |
| CN110975823A (en) * | 2019-12-23 | 2020-04-10 | 徐州工程学院 | Method for desorbing soybean hull heavy metal ion adsorbent |
| CN110975823B (en) * | 2019-12-23 | 2020-12-22 | 徐州工程学院 | Method for desorbing soybean hull heavy metal ion adsorbent |
| CN113385147A (en) * | 2021-07-19 | 2021-09-14 | 西北大学 | Application of composite adsorption material in simultaneous removal of phenol and Cr (VI) in wastewater and method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chaabane et al. | Comparative studies on the adsorption of metal ions from aqueous solutions using various functionalized graphene oxide sheets as supported adsorbents | |
| Xu et al. | Polyoxime-functionalized magnetic nanoparticles for uranium adsorption with high selectivity over vanadium | |
| Fan et al. | Facile synthesis of tea waste/Fe 3 O 4 nanoparticle composite for hexavalent chromium removal from aqueous solution | |
| Huang et al. | Effective removal of Cr (VI) using β-cyclodextrin–chitosan modified biochars with adsorption/reduction bifuctional roles | |
| Xing et al. | NH2-rich polymer/graphene oxide use as a novel adsorbent for removal of Cu (II) from aqueous solution | |
| Ji et al. | Facile synthesis of multiwall carbon nanotubes/iron oxides for removal of tetrabromobisphenol A and Pb (II) | |
| CN102188957B (en) | Polyethyleneimine modified magnetic porous adsorbent and preparation method and application thereof | |
| Wang et al. | Preparation of a functionalized magnetic metal–organic framework sorbent for the extraction of lead prior to electrothermal atomic absorption spectrometer analysis | |
| Afkhami et al. | Alumina nanoparticles grafted with functional groups as a new adsorbent in efficient removal of formaldehyde from water samples | |
| Alonso et al. | Development of an on-line solid phase extraction method based on new functionalized magnetic nanoparticles. Use in the determination of mercury in biological and sea-water samples | |
| Zhou et al. | Chemical pretreatment of rice straw biochar: effect on biochar properties and hexavalent chromium adsorption | |
| Li et al. | The preparation of novel adsorbent materials with efficient adsorption performance for both chromium and methylene blue | |
| Khurshid et al. | Anionic azo dyes removal from water using amine-functionalized cobalt–iron oxide nanoparticles: a comparative time-dependent study and structural optimization towards the removal mechanism | |
| Wang et al. | Preparation of a novel chelating resin containing amidoxime–guanidine group and its recovery properties for silver ions in aqueous solution | |
| Zhu et al. | Poly (N, N-dimethylaminoethyl methacrylate) modification of activated carbon for copper ions removal | |
| Chen et al. | Thiol-grafted magnetic polymer for preconcentration of Cd, Hg, Pb from environmental water followed by inductively coupled plasma mass spectrometry detection | |
| Pan et al. | Controlled synthesis of pentachlorophenol-imprinted polymers on the surface of magnetic graphene oxide for highly selective adsorption | |
| CN107915270A (en) | The method of comprehensive utilization of magnetic polymer material after one kind absorption Cr (VI) | |
| Shao et al. | Retracted Article: Reductive immobilization of uranium by PAAM–FeS/Fe 3 O 4 magnetic composites | |
| Anirudhan et al. | Glutaraldehyde cross-linked epoxyaminated chitosan as an adsorbent for the removal and recovery of copper (II) from aqueous media | |
| Zhao et al. | Self-assembly of a surface bisphenol A-imprinted core–shell nanoring amino-functionalized superparamagnetic polymer | |
| CN112452346A (en) | Universal method for preparing metal single-atom carbon-based catalyst and application | |
| Khaligh et al. | Speciation and determination of inorganic arsenic species in water and biological samples by ultrasound assisted-dispersive-micro-solid phase extraction on carboxylated nanoporous graphene coupled with flow injection-hydride generation atomic absorption spectrometry | |
| CN114832784B (en) | Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof | |
| CN103314021A (en) | Modified poly (styrene-co-maleic anhydride) and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180417 |
|
| RJ01 | Rejection of invention patent application after publication |