CN103803656A - Method of ferrous acid manganese nano material coating crystallizer for extracting byproduct sodium sulfite in naphthol production process by using sulfonation alkali fusion method - Google Patents
Method of ferrous acid manganese nano material coating crystallizer for extracting byproduct sodium sulfite in naphthol production process by using sulfonation alkali fusion method Download PDFInfo
- Publication number
- CN103803656A CN103803656A CN201410027918.5A CN201410027918A CN103803656A CN 103803656 A CN103803656 A CN 103803656A CN 201410027918 A CN201410027918 A CN 201410027918A CN 103803656 A CN103803656 A CN 103803656A
- Authority
- CN
- China
- Prior art keywords
- sodium sulfite
- alkali fusion
- crystallizer
- manganese ferrite
- extracting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method of a ferrous acid manganese nano material coating crystallizer for extracting a byproduct sodium sulfite in the naphthol production process by using a sulfonation alkali fusion method. A ferrous acid manganese nano material is prepared by using an ultraviolet lighting and ultrasonic wave coupling technique in a controllable manner; in the preparation process, ferrous chloride, manganous nitrate, oxalic acid and ethylenediamine tetraacetic acid are taken as reaction raw materials, and distilling water is used as a solvent; as the ferrous acid manganese nano material has unique crystal structural characteristics of unique spinel type ferrite, the activity center with high density is provided in the sodium sulfite crystallization process, and the yield of the sodium sulfite is improved.
Description
[technical field]: the invention belongs to inorganic nano material technology of preparing and inorganic salt and extract field, particularly relate to a kind of Manganese Ferrite nano-material coating crystallizer and produce at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process.
[background technology]:
Naphthols comprises 1-naphthols and beta naphthal, and this class material exists as the critical material of dyestuff intermediate and Organic Chemicals, leather tanning, dyestuff, pigment dyestuff, spices, rubber antioxidant, agricultural chemicals and medical aspect have important application.The synthetic once used method of naphthols has sulfonated alkali fusion method, hydrogen peroxide method, naphthane method, electrochemical process, alpha-naphthylamine hydrolysis method, isopropyl naphthalene method etc.In aforesaid method, it is maximum that sulfonated alkali fusion method uses.Its primary product is S-WAT and sodium naphtholate.S-WAT is because cheap and functionalization has universal use in fields such as electrochemistry, food bleaching agent, chemosynthesis, papermaking, antioxidant photographic developer, process hides, cotton fabric bleaching, medicine intermediate, dyestuffs.But the common method of evaporation of S-WAT extracting method or the method for cooling of traditional sulfonated alkali fusion method.But in the time separating out from mother liquor because being subject to the restriction of service temperature and material viscosity, and make that speed that S-WAT separates out is slow and crystal formation is not good enough, therefore strengthen that to improve crystalline environment be to improve sulfonated alkali fusion method to produce the crystallization rate of naphthols byproduct in process S-WAT and the key point of quality.
Manganese Ferrite nano material, because having unique spinel type ferrite crystalline structure characteristic, can provide highdensity active centre in S-WAT crystallisation process, is expected to improve the productive rate of S-WAT.Especially, but with regard to material is synthetic, conventionally adopt microwave irradiation, high temperature solid-state method, mechanical ball milling method, sol-gel method, coprecipitation method, electrical spinning method, hydrothermal method, micro emulsion method etc. (201310549046.4; Safontseva NY, Nikiforov IY.Phys.Solid State2001,43,61; Sun SH, Zeng H, Robinson DB.J.Am.Chem.Soc.2004,126,273; Wang X, Zhuang J, Peng Q, et al.Nature2005,437,121; Zhang GY, Li CS, Chen J, et al.Sensors Actuators B.2007,120,403; Jia X, Chen DR, Jiao XL, et al.J.Phys.Chem.C2008,112,911; Zhen L, He K, Xu CY, J.Magn.Magn.Mater2008,320,2672; Wang J, Chen QW, Hou BY, et al.Eur.J.Inorg.Chem.2004,1165; Ju YW, Park JH, Jung HR, et al.Compos.Sci.Technol.2008,68,1704; Lee Y, Lee J, Bae CJ, et al.Adv.Funct.Mater.2005,15,503; Ding, J, McCormick, P.G., Street, R., j.Magn.Magn.Mater., 1997,171 (3), 309-314), its synthetic aspect subject matter is that the specific dimension Manganese Ferrite nano material of low cost, scale controlledly synthesis and high strength tack coating also exist certain technical difficulty, and especially less document relates to and adopts the document of the synthetic Manganese Ferrite nano material of ultraviolet illumination and ultrasonic wave coupling technique less.
Produce for sulfonated alkali fusion method the not good enough technical barrier of crystalline environment that in naphthols process, S-WAT extracts, the art of this patent has been invented the synthetic Manganese Ferrite nano material of ultraviolet illumination and ultrasonic wave coupling technique, and is prepared into nano coating and is applied to sulfonated alkali fusion method and produces in naphthols process and extract in the crystallizer of by-product sodium sulfite.The crystallizer with nano material special coating has the effect of catalysis and high reactivity nucleus in S-WAT leaching process.Be all to exist in dilution, acidifying, boiling part although extract S-WAT, all need in solution, efficiently separate out and could effectively separate with mother liquor.S-WAT precipitation process is to have utilized S-WAT to extract in the larger feature of the changes in solubility of differing temps, and concrete technology scheme is to have developed the novel treatment technique that " flash liberation, secondary separation, centrifugation " combines; " dilution " of the technology of the present invention production technique put into dilution pot for the material of alkali fusion after reacting completely, water at the bottom of dilution pot is prepared approximately 3 tons in advance, and this end water has three kinds of sources: the saturated sodium bisulfite solution that (1) centrifugation produces; (2) workshop flue gas cooling waste water; Or (3) ground flushing water.A kind of Manganese Ferrite nano-material coating crystallizer that patent of the present invention provides produces at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process, optimize the kinetic factor that crystal is separated out, have obvious novelty, practicality and novelty, the high efficiency extraction that this technical renovation is by-product sodium sulfite and sizable application performance have been established solid technical foundation.
[summary of the invention]: the content of patent of the present invention is to provide a kind of Manganese Ferrite nano-material coating crystallizer to produce at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process, its feature is take distilled water as solvent, adopt the synthetic Manganese Ferrite nano material of ultraviolet illumination and ultrasonic wave coupling technique, substantive distinguishing features and the novelty of patent of the present invention are: it is short that ultraviolet illumination and ultrasonic wave coupling technique have the reaction times, cost is low, be applicable to the outstanding advantages such as sizable application, in addition this technological line is the essential laws of verifying between low cost Manganese Ferrite nanometer sheet material microscopic appearance and special coating application, optimize at sulfonated alkali fusion method and produce the crystallization rate of extracting by-product sodium sulfite in naphthols process, provide fundamental basis and practical experience for improving S-WAT quality product.
[technical scheme of the present invention]: patent of the present invention relates to a kind of Manganese Ferrite nano-material coating crystallizer and produces at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process, its material composite character is to adopt ultraviolet illumination and the synthetic Manganese Ferrite nano material of ultrasonic wave coupling technique, in preparation process with iron protochloride, manganous nitrate, oxalic acid, ethylenediamine tetraacetic acid (EDTA) is reaction starting material, distilled water is solvent, the internal surface of crystallizer nano coating of the secondary separation of this Application of micron in the operational path that extracts S-WAT is beneficial to S-WAT rapid crystallization, comprise the following steps:
The first, at room temperature, accurately take 1.7900 grams of iron protochloride (FeCl
24H
2o) solid, and add 100 ml distilled waters, 20 milliliters of hexanaphthenes, fully stir and dissolve completely for 5 minutes; Weigh 3.9800 grams of oxalic acid C
2h
2o
4pour in solution of ferrous chloride with 1.0230 grams of ethylenediamine tetraacetic acid (EDTA)s, fully stir 30 minutes until dissolve completely;
The second, continuing under stirring state, employing wavelength is 310nm, and solution is apart from 20 centimetres of light sources, and intensity of illumination is 3000 μ w/cm
2, 30 ℃ of temperature, light application time 1 hour;
Three, measure the manganous nitrate Mn (NO of 1.7900 grams
3)
2solution, is poured in the first step gained solution; And fully stir 15 minutes, it is to react 12 hours in 120 watts, the ultrasonic reactor of temperature 60 C that solution is transferred to ultrasonic power, obtain suspension liquid, use supercentrifuge with 8000 revs/min of rotating speed separate solid products, in washing process, use distilled water, the rinse of ethanol repetitive scrubbing 8 times, then at 75 ℃ freeze-day with constant temperature 12 hours; Solid product in retort furnace under air atmosphere 700 celsius temperature sintering after 4 hours, obtain Manganese Ferrite nano ultrafine powders end.
Through Hitachi S-4800 scanning electron microscope analysis, it is nanometer sheet material at described Manganese Ferrite nano ultrafine powders end, and wherein the thickness of nanometer sheet is that 15-20 nanometer, length are 2～3 microns; Show through XRD x ray diffraction analysis x, the thing of products therefrom is MnFeO mutually
3, its corresponding PDF card number is 75-894, spacer is Ia-3 (no.206), unit cell parameters a:
The internal surface of crystallizer nano coating of described secondary separation; The weight ratio composition of its coating is: Manganese Ferrite nano ultrafine powders end 20%, propyl carbinol thinner 60%, bisphenol A type epoxy resin 10%, polyoxyethylene glycol auxiliary agent 10%, through planetary ball mill, 300 revs/min of mixing obtain even pigment for 0.5 hour, are then coated in secondary separation internal surface of crystallizer, 180 degree oven dry 1 hour.
Described secondary separation is a part of extracting by-product sodium sulfite in synthetic naphthols operation; Synthetic naphthols primary routing comprises that sulfonation, hydrolysis are blown naphthalene, neutralization pot, neutralized cooling, suction strainer, alkali fusion, dilution, flash liberation, acidifying, boil, two boil, three boil, be dried, still pot,, three fraction grooves, cut into slices header tank, slicing machine, wrapping machine, sell outward; Wherein, extract the operational path of S-WAT and be the material after alkali fusion dilution by flash liberation, secondary separation, centrifugation, dry packing as shown in patent accompanying drawing 4, or acidifying material is carried out to flash liberation, secondary separation, centrifugation, dry packing as shown in patent accompanying drawing 5.
[advantage of the present invention and effect]: a kind of Manganese Ferrite nano-material coating of patent of the present invention crystallizer produces at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process, have the following advantages and beneficial effect take iron protochloride, manganous nitrate, oxalic acid, ethylenediamine tetraacetic acid (EDTA) as reaction starting material, distilled water is solvent, adopt ultraviolet illumination and the controlled Manganese Ferrite nano material of preparing of ultrasonic wave coupling technique, the internal surface of crystallizer nano coating of the secondary separation of this Application of micron in the operational path that extracts S-WAT; Synthetic nano material size homogeneous, Stability Analysis of Structures, will represent even more important active effect in Application Areas.
[accompanying drawing explanation]:
Fig. 1 is scanning electronic microscope (SEM) figure of synthetic Manganese Ferrite nanometer sheet
Fig. 2 is scanning electronic microscope (SEM) figure of synthetic Manganese Ferrite nanometer sheet
Fig. 3 is the X-ray diffraction analysis spectrogram of synthetic Manganese Ferrite sample
Fig. 4 adopts novel sulfonated alkali fusion technique to extract the detail flowchart of S-WAT in alkali fusion dilution operation
Fig. 5 adopts novel sulfonated alkali fusion technique to extract the detail flowchart of S-WAT at acidizing process
[embodiment]:
Embodiment 1: adopt the synthetic Manganese Ferrite nanometer sheet material of ultraviolet illumination and ultrasonic wave coupling technique
The first, at room temperature, accurately take 1.7900 grams of iron protochloride (FeCl
24H
2o) solid, and add 100 ml distilled waters, 20 milliliters of hexanaphthenes, fully stir and dissolve completely for 5 minutes; Weigh 3.9800 grams of oxalic acid C
2h
2o
4pour in solution of ferrous chloride with 1.0230 grams of ethylenediamine tetraacetic acid (EDTA)s, fully stir 30 minutes until dissolve completely; The second, continuing under stirring state, employing wavelength is 310nm, and solution is apart from 20 centimetres of light sources, and intensity of illumination is 3000 μ w/cm
2, 30 ℃ of temperature, light application time 1 hour; Three, measure the manganous nitrate Mn (NO of 1.7900 grams
3)
2solution, is poured in the first step gained solution; And fully stir 15 minutes, it is to react 12 hours in 120 watts, the ultrasonic reactor of temperature 60 C that solution is transferred to ultrasonic power, obtain suspension liquid, use supercentrifuge with 8000 revs/min of rotating speed separate solid products, in washing process, use distilled water, the rinse of ethanol repetitive scrubbing 8 times, then at 75 ℃ freeze-day with constant temperature 12 hours; Solid product in retort furnace under air atmosphere 700 celsius temperature sintering after 4 hours, obtain Manganese Ferrite nano ultrafine powders end.It is nanometer sheet material for gained Manganese Ferrite nano ultrafine powders end Hitachi S-4800 scanning electron microscope analysis, and wherein the thickness of nanometer sheet is that 15-20 nanometer, length are 2～3 microns (Fig. 1-2); Show through XRD x ray diffraction analysis x, the thing of products therefrom is MnFeO mutually
3, its corresponding PDF card number is 75-894, spacer is Ia-3 (no.206), unit cell parameters a:
(Fig. 3).
Embodiment 2: the coating preparation of Manganese Ferrite nanometer sheet material
Manganese Ferrite nano ultrafine powders end is coated in to the reactor internal surface of secondary separation; First weigh material according to weight ratio composition: Manganese Ferrite nano ultrafine powders end 20%, propyl carbinol thinner 60%, bisphenol A type epoxy resin 10%, polyoxyethylene glycol auxiliary agent 10%, through planetary ball mill, 300 revs/min of mixing obtain even pigment for 0.5 hour, are then coated in secondary separation internal surface of crystallizer, 180 degree oven dry 1 hour.
Embodiment 3: the coating of Manganese Ferrite nano material is the application of the feed separation after alkali fusion dilution in the operational path that extracts S-WAT
The reactor internal surface nano coating of prepared secondary separation in embodiment 2, secondary separation is a part of extracting by-product sodium sulfite in synthetic naphthols operation; Synthetic naphthols primary routing comprises that sulfonation, hydrolysis are blown naphthalene, neutralization pot, neutralized cooling, suction strainer, alkali fusion, dilution, flash liberation, acidifying, boil, two boil, three boil, be dried, still pot,, three fraction grooves, cut into slices header tank, slicing machine, wrapping machine, sell outward; Wherein, the operational path of extraction S-WAT is by the flash liberation, secondary separation, centrifugation, the dry packing that are illustrated in fig. 4 shown below to the material after alkali fusion dilution.
Embodiment 4: the coating of Manganese Ferrite nano material is the application of the feed separation after acidulants material process in the operational path that extracts S-WAT
The reactor internal surface nano coating of prepared secondary separation in embodiment 2, secondary separation is a part of extracting by-product sodium sulfite in synthetic naphthols operation; Synthetic naphthols primary routing comprises that sulfonation, hydrolysis are blown naphthalene, neutralization pot, neutralized cooling, suction strainer, alkali fusion, dilution, flash liberation, acidifying, boil, two boil, three boil, be dried, still pot,, three fraction grooves, cut into slices header tank, slicing machine, wrapping machine, sell outward; Wherein, extract the operational path of S-WAT be acidulants material process is illustrated in fig. 5 shown below carry out flash liberation, secondary separation, centrifugation, dry packing.
Claims (4)
1. patent of the present invention relates to a kind of Manganese Ferrite nano-material coating crystallizer and produces at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process, its material composite character is to adopt ultraviolet illumination and the synthetic Manganese Ferrite nano material of ultrasonic wave coupling technique, in preparation process take iron protochloride, manganous nitrate, oxalic acid, ethylenediamine tetraacetic acid (EDTA) as reaction starting material, distilled water is solvent, and the internal surface of crystallizer nano coating of the secondary separation of this Application of micron in the operational path that extracts S-WAT is beneficial to S-WAT rapid crystallization; Comprise the following steps:
The first, at room temperature, accurately take 1.7900 grams of iron protochloride (FeCl
24H
2o) solid, and add 100 ml distilled waters, 20 milliliters of hexanaphthenes, fully stir and dissolve completely for 5 minutes; Weigh 3.9800 grams of oxalic acid C
2h
2o
4pour in solution of ferrous chloride with 1.0230 grams of ethylenediamine tetraacetic acid (EDTA)s, fully stir 30 minutes until dissolve completely;
The second, continuing under stirring state, employing wavelength is 310nm, and solution is apart from 20 centimetres of light sources, and intensity of illumination is 3000 μ w/cm
2, 30 ℃ of temperature, light application time 1 hour;
Three, measure the manganous nitrate Mn (NO of 1.7900 grams
3)
2solution, is poured in the first step gained solution; And fully stir 15 minutes, it is to react 12 hours in 120 watts, the ultrasonic reactor of temperature 60 C that solution is transferred to ultrasonic power, obtain suspension liquid, use supercentrifuge with 8000 revs/min of rotating speed separate solid products, in washing process, use distilled water, the rinse of ethanol repetitive scrubbing 8 times, then at 75 ℃ freeze-day with constant temperature 12 hours; Solid product in retort furnace under air atmosphere 700 celsius temperature sintering after 4 hours, obtain Manganese Ferrite nano ultrafine powders end.
2. a kind of Manganese Ferrite nano-material coating crystallizer produces at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process according to claim 1, it is characterized in that: through Hitachi S-4800 scanning electron microscope analysis, it is nanometer sheet material at described Manganese Ferrite nano ultrafine powders end, and wherein the thickness of nanometer sheet is that 15-20 nanometer, length are 2～3 microns; Show through XRD x ray diffraction analysis x, the thing of products therefrom is MnFeO mutually
3, its corresponding PDF card number is 75-894, spacer is Ia-3 (no.206), unit cell parameters a:
3. a kind of Manganese Ferrite nano-material coating crystallizer produces at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process according to claim 1, it is characterized in that: the internal surface of crystallizer nano coating of described secondary separation; The weight ratio composition of its coating is: Manganese Ferrite nano ultrafine powders end 20%, propyl carbinol thinner 60%, bisphenol A type epoxy resin 10%, polyoxyethylene glycol auxiliary agent 10%, through planetary ball mill, 300 revs/min of mixing obtain even pigment for 0.5 hour, are then coated in secondary separation internal surface of crystallizer, 180 degree oven dry 1 hour.
4. a kind of Manganese Ferrite nano-material coating crystallizer produces at sulfonated alkali fusion method the method for extracting by-product sodium sulfite in naphthols process according to claim 1, it is characterized in that: described secondary separation is a part of extracting by-product sodium sulfite in synthetic naphthols operation; Synthetic naphthols primary routing comprises that sulfonation, hydrolysis are blown naphthalene, neutralization pot, neutralized cooling, suction strainer, alkali fusion, dilution, flash liberation, acidifying, boil, two boil, three boil, be dried, still pot,, three fraction grooves, cut into slices header tank, slicing machine, wrapping machine, sell outward; Wherein, extract the operational path of S-WAT and be the material after alkali fusion dilution by flash liberation, secondary separation, centrifugation, dry packing as shown in patent accompanying drawing 4, or acidifying material is carried out to flash liberation, secondary separation, centrifugation, dry packing as shown in patent accompanying drawing 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410027918.5A CN103803656A (en) | 2014-01-22 | 2014-01-22 | Method of ferrous acid manganese nano material coating crystallizer for extracting byproduct sodium sulfite in naphthol production process by using sulfonation alkali fusion method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410027918.5A CN103803656A (en) | 2014-01-22 | 2014-01-22 | Method of ferrous acid manganese nano material coating crystallizer for extracting byproduct sodium sulfite in naphthol production process by using sulfonation alkali fusion method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103803656A true CN103803656A (en) | 2014-05-21 |
Family
ID=50701107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410027918.5A Pending CN103803656A (en) | 2014-01-22 | 2014-01-22 | Method of ferrous acid manganese nano material coating crystallizer for extracting byproduct sodium sulfite in naphthol production process by using sulfonation alkali fusion method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103803656A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826731A (en) * | 1994-07-08 | 1996-01-30 | Tdk Corp | Production of ferrite material |
| CN102303911A (en) * | 2011-08-12 | 2012-01-04 | 湖州师范学院 | Microwave preparation method of cerium ferrate nano powder |
| CN103341346A (en) * | 2013-06-26 | 2013-10-09 | 江苏省环境科学研究院 | Preparation method of manganese ferrite nanoparticle-graphene compound |
| CN103482706A (en) * | 2013-10-15 | 2014-01-01 | 大连交通大学 | Hollow spherical nano manganese ferrite, and preparation method and application thereof |
-
2014
- 2014-01-22 CN CN201410027918.5A patent/CN103803656A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826731A (en) * | 1994-07-08 | 1996-01-30 | Tdk Corp | Production of ferrite material |
| US5750045A (en) * | 1994-07-08 | 1998-05-12 | Tdk Corporation | Preparation of ferrite materials |
| CN102303911A (en) * | 2011-08-12 | 2012-01-04 | 湖州师范学院 | Microwave preparation method of cerium ferrate nano powder |
| CN103341346A (en) * | 2013-06-26 | 2013-10-09 | 江苏省环境科学研究院 | Preparation method of manganese ferrite nanoparticle-graphene compound |
| CN103482706A (en) * | 2013-10-15 | 2014-01-01 | 大连交通大学 | Hollow spherical nano manganese ferrite, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 唐清: ""2-萘酚生产中无机盐废液的回收利润"", 《天津化工》, no. 3, 31 December 1998 (1998-12-31), pages 34 - 35 * |
| 郑立红等: ""磺化法苯酚生产中副产物亚硫酸钠的脱酚"", 《氯碱工业》, no. 5, 31 May 2001 (2001-05-31), pages 29 - 30 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102897724B (en) | Tin selenide nano-flowers and preparation method thereof | |
| Ma et al. | Microwave synthesis of cellulose/CuO nanocomposites in ionic liquid and its thermal transformation to CuO | |
| Luitel et al. | Highly efficient NIR to NIR upconversion of ZnMoO 4: Tm 3+, Yb 3+ phosphors and their application in biological imaging of deep tumors | |
| CN108529604A (en) | A kind of preparation method of graphene quantum dot | |
| CN102649589B (en) | Fibroin-controlled alpha type ferric oxide nano material and preparation method thereof | |
| Pu et al. | Process intensification for scalable synthesis of ytterbium and erbium co-doped sodium yttrium fluoride upconversion nanodispersions | |
| CN105502373A (en) | Environment-friendly preparing method of graphene | |
| Thirumalai et al. | Controlled synthesis, formation mechanism and lumincence properties of novel 3-dimensional Gd 2 (MoO 4) 3: Eu 3+ nanostructures | |
| CN102745749B (en) | Preparation method for nanometer Mn3O4 particles | |
| CN107098341A (en) | Graphene oxide new type water thermal stencil agent and its preparation method of nano composite material | |
| CN109369057A (en) | A kind of microcapsules chloride ion curing agent and its preparation method and application | |
| CN102660258B (en) | Method for preparing water-soluble CdS quantum dot | |
| CN105948117A (en) | Hydrothermal method for preparing HfO2 nano-particles | |
| CN106966430B (en) | A kind of preparation method of metal vanadate nano material | |
| CN105776253A (en) | Method for preparing potassium nitrate and nanometer kaolinite with kaliophilite powder bodies | |
| CN110182786B (en) | Method for preparing self-doped sulfur fluorescent carbon nanodots by using lignosulfonate | |
| CN112408475A (en) | Preparation of rare earth doped NaBiF by ultrasonic solution method4Method for preparing nanoparticles and application thereof | |
| CN103803656A (en) | Method of ferrous acid manganese nano material coating crystallizer for extracting byproduct sodium sulfite in naphthol production process by using sulfonation alkali fusion method | |
| CN106517299A (en) | Flaky self-assembled basic copper carbonate flower ball and simple preparation method thereof | |
| CN104014338B (en) | Solid base carrier thallium catalyst and preparation method | |
| CN102275973A (en) | Preparation method of basic copper carbonate microspheres | |
| CN110563036A (en) | bismuth oxide nano material rich in oxygen vacancy and preparation method thereof | |
| CN105460899B (en) | A kind of preparation method of the exfoliated layered double-hydroxide of high concentration | |
| CN105253915A (en) | Preparation method of Zn2(OH)3VO3 micro-sphere | |
| CN101811729A (en) | Method for preparing rice-granule nano ZnO |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140521 |