CN106423044A - Method for preparing polymerized nanomaterial with kaolin used as matrix - Google Patents
Method for preparing polymerized nanomaterial with kaolin used as matrix Download PDFInfo
- Publication number
- CN106423044A CN106423044A CN201610959094.4A CN201610959094A CN106423044A CN 106423044 A CN106423044 A CN 106423044A CN 201610959094 A CN201610959094 A CN 201610959094A CN 106423044 A CN106423044 A CN 106423044A
- Authority
- CN
- China
- Prior art keywords
- kaolin
- ldh
- phosphorus
- natural
- nanometer material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a method for preparing a polymerized nanomaterial with kaolin used as a matrix. An Mg/Al LDH (layered double hydroxide) is prepared and loaded with natural kaolin or thermal modified kaolin, LDH loaded natural kaolin and LDH loaded thermal modified kaolin are prepared, the dominant clay mineral composition of kaolin is kaolinite, the kaolin has resource attributes such as higher plasticity, higher fire resistance, good insulativity, chemical stability and the like, so that the kaolin is applied to the fields of ceramic, refractory materials, rubber, medicine, cosmetics and the like for a long time, and there are more research on organic pollutants and heavy metal adsorption in the environmental field but little research on adsorption of phosphorus. The kaolin with greater adsorption potential is modified with LDHs, and the application of kaolin in wastewater is improved.
Description
Technical field
The invention belongs to polymer/nanometer field of material preparation, particularly to one kind with Kaolin as matrix, double hydrogen with stratiform
The preparation method of oxide synthetically prepared waste water of livestock poultry phosphorus adsorbent, the poultry contaminated wastewater being applied to high phosphorus concentration controls.
Background technology
Layered double-hydroxide (Layered Double Hydroxides, abbreviation LDHs) i.e. brucite or anion are glued
Soil, its basic structural formula is：M2+ 1-xM3+ x(OH)2(An-)x/n·mH2O, wherein M2+And M3+Represent respectively bivalence and trivalent sun from
Son, An-Represent n valency anion.LDHs has the layer structure of similar shepardite, in the construction unit layer of shepardite, bivalence sun
Ionic portions are substituted by Tricationic, produce structure positive charge, thus need introducing anion to enter construction unit interlayer putting down
Weighing apparatus structure positive charge.It is in the anion of structure interlayer and structure positive charge belongs to long-range electrostatic balance, active force is weaker, wherein
Anion can be by other anion exchanges, thus LDHs has excellent anion exchange performance.
In recent years, the research that LDHs carries out in water process is more, particularly makees adsorbent and passes through surface adsorption and interlayer
Anion exchange processes the high price oxo-anions groups such as phosphorous acid group, arsenate, selenate radical, chromate and shows preferable effect
Really.LDHs has higher cation exchange capacity (CEC), and wherein Mg～Al ratio is during for 2, stronger to the removal ability of phosphorus, simultaneously heat modification
Impact be there is also on the phosphorus absorption property of Mg～Al layered double-hydroxide.But the LDHs of routine exists prominent in actual applications
Problem, mainly due to its crystal maximum gauge and minimum diameter ratio typically between 1～3, crystal particle diameter is generally 0.1
～0.15 μm, brilliant bundle size is usually 1～100 μm, and such nominal particle size makes it have colloidal dispersions performance, in water body, especially
, in current water, elimination of being sorry removes for it, thus exists in actual applications compared with big limitation.
Content of the invention
It is an object of the invention to provide a kind of method that polymer/nanometer material is prepared for matrix with Kaolin, it is applied to high phosphorus
The poultry contaminated wastewater of concentration controls.
For reaching above-mentioned purpose, the technical scheme that the present invention provides is：
A kind of method preparing polymer/nanometer material for matrix with Kaolin, comprises the following steps：
The synthesis of (a) Mg/Al layered double-hydroxide：
Prepare NaOH solution, dropwise instill equipped with MgCl2And AlCl3In the vinyon bottle of mixed solution, stirring 1～
It is positioned over after 4h aging 2～6 days in 60～105 DEG C of constant temperature ovens；Product is centrifuged after being cooled to room temperature, and precipitation uses distilled water water
It is washed till no Cl-Exist, dry then at 60～105 DEG C, it is standby that 100 mesh excessively store in polyethylene bottle；
C () LDH loads kaolinic preparation：
Weigh Kaolin, after being scattered in stirring 12～36h in distilled water, add LDH to continue stirring 12～36h；Clay hangs
After liquid centrifugation, precipitation is washed 4～8 times with distilled water, and product is dried in 60～105 DEG C, crosses 100 mesh standby；
According to described step (a) and step (c), prepared LDH loads natural kaolin, i.e. LDH-NKL.
Further, also have between described step (a) and step (c) and natural kaolin is carried out thermally-denatured step
(b)：
(b) natural kaolin heat modification：
Take natural kaolin to calcine 1～4h at 500～600 DEG C in Muffle furnace, take out cooling, cross 100 mesh sieves, obtain hot
Modified kaolin；
According to described step (a), step (b) and step (c), prepared LDH loads heat modification Kaolin, i.e. LDH-NKL；
Wherein, in step (a), the concentration range of NaOH solution is 1.0～3.0mol/L, MgCl2And AlCl3Mixing
Solution concentration scope is 1.0～3.0mol/L, Mg2+/Al3+=3.0.
Wherein, in step (a), titration and whipping process mixture reaction temperature control are at 20 ± 1 DEG C.
Wherein, in step (c), described distilled water is kaolinic 20～30 times of volumes；Described Kaolin and the matter of LDH
Amount is 3 than scope：1～6：1.
LDHs is supported on environment mineral material the present invention, not only can improve the absorption property to phosphorus for the environmental mineral,
And removal in water body for the LDHs can be solved the problems, such as.
Kaolinic leading clay mineral content is kaolinite, and it has stronger plasticity, higher fire resistance, good
Insulating properties and the Resource Properties such as chemical stability, thus be used in pottery, refractory material, rubber, medicine, cosmetics for a long time
Deng field, the research in terms of environmental area is used for organic pollution and heavy metal adsorption is also more, but rare to phosphorus adsorptivity
The research of energy.The present invention is modified by the Kaolin larger to absorption property potentiality using LDHs, improves Kaolin useless
Application in water.
Brief description
Fig. 1：LDH loads the absorption property to phosphorus for the Kaolin.
Fig. 2：LDH loads the adsorption isothermal curve to phosphorus for the Kaolin.
Fig. 3：LDH loads the dynamic absorption curve to phosphorus for the Kaolin.
Specific embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1：The synthesis of Mg/Al layered double-hydroxide (LDH)：
Accurately prepare the NaOH solution of 2.0mol/L, dropwise instill the MgCl equipped with 1.0mol/L2And AlCl3(Mg2+/Al3+
=3.0), in the vinyon bottle of mixed solution, after stirring 3h, (titration and whipping process mixture reaction temperature control are 20
(± 1) DEG C) it is positioned over aging 4 days in 65 DEG C of constant temperature ovens.Product is centrifuged after being cooled to room temperature, and precipitation distilled water is washed to
No Cl-There is (AgNO3Check), dry then at 65 DEG C, it is standby that 100 mesh excessively store in polyethylene bottle.
Embodiment 2：LDH loads the preparation of natural kaolin (LDH-NKL)：
Accurately weigh 20g natural kaolin to be scattered in 500mL distilled water, after stirring 24h, add 5.0g embodiment 1 institute
Prepared LDH continues stirring 24h.After the centrifugation of clay suspension, precipitation is washed 5 times with distilled water, and product is dried in 65 DEG C, crosses 100 mesh
Standby.
Embodiment 3：LDH loads the preparation of heat modification Kaolin (LDH-HKL)：
Take 100g natural kaolin to calcine 2h at 500 DEG C in Muffle furnace, take out cooling, cross 100 mesh sieves, obtain heat modification
Sample.
Accurately weigh 20g to be scattered in 500mL distilled water through 500 DEG C of thermally-denatured Kaolin, after stirring 24h, add
LDH obtained by 5.0g embodiment 1 continues stirring 24h.After the centrifugation of clay suspension, precipitation is washed 5 times with distilled water, and product is in 65 DEG C
Dry, cross 100 mesh standby.
To natural with prepared in modified kaolin and embodiment LDH load natural kaolin, LDH load heat modification kaolinite
The chemical composition of soil is measured, and the results are shown in Table 1.
The natural chemical composition (mass percent) with modified kaolin of table 1
Embodiment 4：The impact to Kaolin phosphorus absorption property for the LDH load：
Accurately weigh LDH-NKL the and LDH-HKL sample 0.5g that LDH and embodiment 2,3 be obtained in 150mL centrifuge tube,
50mL is added to be the simulated wastewater solution of 20mg/L containing phosphorus concentration, constant temperature (200r/min, (20 ± 1) DEG C) concussion 24h, 4
000r/min is centrifuged 10min, and molybdenum blue colorimetric method measures the content of phosphorus, draws adsorption curve (Fig. 1).It was found that 3 kinds of samples exist
Under the conditions of phosphorus concentration is 20mg/L, to the absorbability of phosphorus quite, all in 1.9mg/g, the clearance of phosphorus is all for phosphorus adsorbance
For 95% about.3 kinds of samples are all preferable to the treatment effect of phosphorus, and residual solution phosphorus concentration is 1mg/L, are all less than China《Poultry
Aquaculture pollutant emission standard》The discharge standard of middle phosphorus.3 kinds of sample treatment effects are no significantly different, mainly due to 3 kinds of samples
Product are all relatively strong to the absorption property of phosphorus, and it is 20mg L that its saturated extent of adsorption is far above 50mL phosphorus concentration-1Simulated wastewater in phosphorus
Content, thus fail to show between LDH, LDH-NKL and LDH-HKL sample to the absorbability of phosphorus and the difference of the rate of adsorption
Different, but LDHs load Kaolin is more natural and heat modification Kaolin substantially increases to the absorption property of phosphorus.
Embodiment 5：LDH loads Kaolin and the maximum adsorption capacity of phosphorus is tested：
Accurately weigh natural kaolin sample 0.5g in 150mL centrifuge tube, add 50mL contain phosphorus concentration be 0,3,6,10,
30th, 50,80,100,120,140,160,180, the simulated wastewater solution of 200mg/L.Constant temperature oscillation 24h, remaining step ibid,
Draw phosphorus element adsorption isothermal curve (Fig. 2).Accurately weigh LDH-NKL the and LDH-HKL sample that LDH and embodiment 2,3 are obtained
0.5g in 150mL centrifuge tube, add 50mL contain phosphorus concentration be 0,3,6,10,30,50,80,100,120,140,160,180,
200th, 250,300,400,500, the simulated wastewater solution of 600mg/L.Constant temperature oscillation 24h, remaining step ibid, draws phosphorus element etc.
Warm adsorption curve (Fig. 2).As shown in Figure 2, LDH and LDH loads the adsorption curve to phosphorus for the heat modification Kaolin, changes with natural and heat
Property kaolinic consistent, that is, with the increase of phosphorus concentration, the slope of curve, by being gradually reduced greatly, finally tends to balance.It can be seen that, with
LDH and the increase to phosphorus adsorbance for the LDH-HKL, it is gradually lowered to the absorption affinity ability of phosphorus.And LDH load natural kaolin
To the absorption of phosphorus with phosphorus concentration increase, at first the slope of curve increase, gradually gentle afterwards, and the later stage starts to be slowly increased and
Reach balance eventually, strengthen again after equilibration had been achieved, show multilayer adsorption feature.It is respectively in phosphorus initial concentration
When 600mg/L, 400mg/L and 400mg/L, LDH, LDH-NKL and LDH-HKL respectively may be about to the saturated extent of adsorption of phosphorus
19.2mg/g, 10.2mg/g and 10.3mg/g, during balance, solution phosphorus concentration is respectively 408mg/L, 296mg/L and 297mg/L.Table
The saturated extent of adsorption higher (19.2mg/g) (Fig. 2) to phosphorus for the bright LDHs.LDH-NKL and LDH-HKL improves compared with natural kaolin
Nearly 10 times, improve about 2 times compared with 500 DEG C of heat modification Kaolin.The Financial cost of comprehensive product preparation, ease-to-operate and phosphorus
Absorption property, LDH-NKL shows more excellent combination property as phosphorus adsorbing material.
Embodiment 6：LDH loads kaolinic phosphorus adsorption characteristic：
Accurately weigh LDH-NKL the and LDH-HKL sample 0.5g that LDH and embodiment 2,3 be obtained in 150mL centrifuge tube,
Add the simulated wastewater solution that 50mL phosphorus concentration is 20mg/L, under the conditions of constant temperature (20 ± 1) DEG C, 200r/min shakes 0 respectively,
20min, 40min, 1h, 2h, 4h, 6h, 8h, 16h, 24h, remaining step ibid, draws soil phosphorus levels dynamic curve (Fig. 3).Fig. 3
Display, initial period increases to the adsorbance of phosphorus therewith with the increase in response time, 3 kinds of samples, but increased speed is gradually
Slow down, be finally reached balance.LDH, LDH-NKL and LDH-HKL sample is all very fast to the adsorption reaction speed of phosphorus, when proceeding to 2h
Tend to balance, LDH-NKL and LDH-HKL all can comparatively fast complete the adsorption cleaning of phosphorus polluted-water, and adsorbance sample is about
To 1.9mg/g, but from economic considerations, LDH load natural kaolin Financial cost is lower.
The above, be only presently preferred embodiments of the present invention, and not the present invention is made with any pro forma restriction, any ripe
Know professional and technical personnel, in the range of without departing from technical solution of the present invention, according to the technical spirit of the present invention, to above reality
Apply any simple modification, equivalent and improvement that example is made etc., all still fall within technical solution of the present invention protection domain it
Interior.
Claims (6)
1. a kind of with Kaolin for matrix prepare polymer/nanometer material method it is characterised in that：Comprise the following steps：
The synthesis of (a) Mg/Al layered double-hydroxide：
Prepare NaOH solution, dropwise instill equipped with MgCl2And AlCl3In the vinyon bottle of mixed solution, after stirring 1～4h
It is positioned over aging 2～6 days in 60～105 DEG C of constant temperature ovens；Product is centrifuged after being cooled to room temperature, and precipitation distilled water is washed to
No Cl-Exist, dry then at 60～105 DEG C, it is standby that 100 mesh excessively store in polyethylene bottle；
C () LDH loads kaolinic preparation：
Weigh Kaolin, after being scattered in stirring 12～36h in distilled water, add LDH to continue stirring 12～36h；Clay suspension from
After the heart, precipitation is washed 4～8 times with distilled water, and product is dried in 60～105 DEG C, crosses 100 mesh standby；
According to described step (a) and step (c), prepared LDH loads natural kaolin, i.e. LDH-NKL.
2. as claimed in claim 1 with Kaolin for matrix prepare polymer/nanometer material method it is characterised in that：
Also have between described step (a) and step (c) and natural kaolin is carried out thermally-denatured step (b)：
(b) natural kaolin heat modification：
Take natural kaolin to calcine 1～4h at 500～600 DEG C in Muffle furnace, take out cooling, cross 100 mesh sieves, obtain heat modification
Kaolin；
According to described step (a), step (b) and step (c), prepared LDH loads heat modification Kaolin, i.e. LDH-NKL.
3. as claimed in claim 1 with Kaolin for matrix prepare polymer/nanometer material method it is characterised in that：Step
A, in (), the concentration range of NaOH solution is 1.0～3.0mol/L, MgCl2And AlCl3Mixed solution concentration range be 1.0～
3.0mol/L, Mg2+/Al3+=3.0.
4. as claimed in claim 1 with Kaolin for matrix prepare polymer/nanometer material method it is characterised in that：Step
A, in (), titration and whipping process mixture reaction temperature control are at 20 ± 1 DEG C.
5. as claimed in claim 1 with Kaolin for matrix prepare polymer/nanometer material method it is characterised in that：Step
C, in (), described distilled water is kaolinic 20～30 times of volumes；Described Kaolin is 3 with the quality of LDH than scope：1～6：1.
6. the polymer/nanometer material of claim 1 methods described preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959094.4A CN106423044A (en) | 2016-11-03 | 2016-11-03 | Method for preparing polymerized nanomaterial with kaolin used as matrix |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959094.4A CN106423044A (en) | 2016-11-03 | 2016-11-03 | Method for preparing polymerized nanomaterial with kaolin used as matrix |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106423044A true CN106423044A (en) | 2017-02-22 |
Family
ID=58180139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610959094.4A Pending CN106423044A (en) | 2016-11-03 | 2016-11-03 | Method for preparing polymerized nanomaterial with kaolin used as matrix |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423044A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121758A (en) * | 2020-09-14 | 2020-12-25 | 江苏开放大学（江苏城市职业学院） | Layered double hydroxide composite attapulgite clay and preparation method thereof |
| CN115382549A (en) * | 2022-08-05 | 2022-11-25 | 浙江工业大学 | Kaolin-based hydrotalcite composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104614A (en) * | 1985-07-05 | 1987-04-22 | 陶氏化学公司 | Mixed metal layer hydroxide compound-clay adducts as the thickening material of water and other hydrophylic fluids |
| CN1919447A (en) * | 2006-08-16 | 2007-02-28 | 天津化工研究设计院 | Preparation process of flue gas desulfurization and denitration material |
| CN105170076A (en) * | 2015-07-14 | 2015-12-23 | 江苏城市职业学院 | Montmorillonite-based layered double hydroxide polymerization nanometer material, preparation and applications thereof |
-
2016
- 2016-11-03 CN CN201610959094.4A patent/CN106423044A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104614A (en) * | 1985-07-05 | 1987-04-22 | 陶氏化学公司 | Mixed metal layer hydroxide compound-clay adducts as the thickening material of water and other hydrophylic fluids |
| CN1919447A (en) * | 2006-08-16 | 2007-02-28 | 天津化工研究设计院 | Preparation process of flue gas desulfurization and denitration material |
| CN105170076A (en) * | 2015-07-14 | 2015-12-23 | 江苏城市职业学院 | Montmorillonite-based layered double hydroxide polymerization nanometer material, preparation and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周祥博等: "镁铝双氢氧化物和镁铝双氢氧化物负载型高岭土对水体中Cr（VI）的吸附性能研究", 《淮北师范大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121758A (en) * | 2020-09-14 | 2020-12-25 | 江苏开放大学（江苏城市职业学院） | Layered double hydroxide composite attapulgite clay and preparation method thereof |
| CN115382549A (en) * | 2022-08-05 | 2022-11-25 | 浙江工业大学 | Kaolin-based hydrotalcite composite material and preparation method and application thereof |
| CN115382549B (en) * | 2022-08-05 | 2023-11-03 | 浙江工业大学 | Kaolin-based hydrotalcite-like composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gai et al. | Synthesis of magnetic, up‐conversion luminescent, and mesoporous core–shell‐structured nanocomposites as drug carriers | |
| CN105251445A (en) | Porous carbon adsorbent as well as preparation method and application thereof | |
| Abu-Eishah | Removal of Zn, Cd, and Pb Ions from water by Sarooj clay | |
| CN109569548B (en) | Magnetic nano functional material for extracting uranium from seawater and preparation method thereof | |
| CN109289814B (en) | Magnetic carbon aerogel for adsorbing antibiotics in wastewater and preparation method thereof | |
| CN106423044A (en) | Method for preparing polymerized nanomaterial with kaolin used as matrix | |
| CN107029659A (en) | A kind of tri compound bentone soil material and its preparation method and application | |
| WO2022193674A1 (en) | Magadiite/polypyrrole adsorption material for treating rhodamine b wastewater and preparation method and application of magadiite/polypyrrole adsorption material | |
| CN110172263A (en) | Inorganic mineral coating and preparation method thereof | |
| CN114849650A (en) | Preparation method and application of double-surface-characteristic magnetically-modified zirconium MOFs adsorbent | |
| CN114566303B (en) | Preparation method of modified diopside glass solidified body containing molybdenum-containing radioactive waste | |
| WO2018037914A1 (en) | Fluorescent substance and resin composition containing same | |
| Lima et al. | Some consequences of the fluorination of brucite-like layers in layered double hydroxides: Adsorption | |
| CN112574504B (en) | Aerogel prepared by boron mud waste, flame retardant and modification application of aerogel | |
| CN106179193A (en) | A kind of polymerization iron carbonyl modified kaolin composite and its preparation method and application | |
| CN106964315B (en) | A kind of preparation method and application of hollow magnetic Co/ carbon nanotube | |
| Qu et al. | Poly (p-phenylenevinylene) functionalized fluorescent mesoporous silica nanoparticles for drug release and cell imaging | |
| Ansari et al. | Toxicity response of highly colloidal, bioactive, monodisperse SiO2@ Pr (OH) 3 hollow microspheres | |
| CN115677923B (en) | Pre-crosslinked gel particle plugging agent and preparation method and application thereof | |
| CN104058618A (en) | Method for preparing nanoscale cement | |
| CN101338190B (en) | Method for coating surface of strontium aluminate long persistence luminescent powder | |
| CN111423747B (en) | Porous powder capable of releasing negative ions and far infrared rays and application thereof | |
| CN104650303B (en) | A kind of preparation method for being modified oil-filled high-performance powder butadiene-styrene rubber | |
| Xu et al. | Calcined Oil Shale Semi-coke for Significantly Improved Performance Alginate-Based Film by Crosslinking with Ca 2+ | |
| CN112111977B (en) | Flame-retardant transition metal oxide sepiolite composite material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20170222 |