CN104817094B - Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method - Google Patents
Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method Download PDFInfo
- Publication number
- CN104817094B CN104817094B CN201510198818.3A CN201510198818A CN104817094B CN 104817094 B CN104817094 B CN 104817094B CN 201510198818 A CN201510198818 A CN 201510198818A CN 104817094 B CN104817094 B CN 104817094B
- Authority
- CN
- China
- Prior art keywords
- microsphere
- hydrothermal
- anhydrous
- multistage porous
- synthetic method
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method. The method comprises the steps of adding aqueous alkali into a calcium salt solution, adding borate solid powder into the mixture, supplementing water and performing stirring; putting the obtained slurry in a hydrothermal reaction kettle, raising the temperature to enable the slurry to be reacted, and washing, filtering and drying hydrothermal products to obtain hydration calcium borate (Ca4B10O19. 7H2O) microspheres; putting the microspheres in a roaster to be roasted, washing, filtering and drying the roasted microspheres to obtain anhydrous multistage porous calcium borate (Ca (BO2)2) microspheres. By the aid of the method, hydrothermal controllable preparation of Ca4B10O19.7H2O is achieved, subsequent medium-temperature roasting of hydrothermal products is used for achieving crystal water removal to obtain three-dimensional anhydrous multistage porous Ca (BO2)2 microspheres. The method has the advantages of being simple to operate, mild in condition, cheap and easy to obtain in material, capable of not adding any additives and the like and easy to produce industrially.
Description
Technical field
The present invention relates to a kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, belong to inorganic chemical technology technical field.
Background technology
In recent years, three-dimensional multistage porous material enjoys researcher to favor because the advantages such as its structure is unique, specific surface area is big, density is little are widely used to the fields such as electrochemistry, organic catalysis, sewage disposal.But, three-dimensional multistage porous material currently mainly utilizes hydro-thermal method and solvent structure, and hydro-thermal method generally requires addition template or derivant in reaction system and assists it to grow, but the addition of template/derivant not only can bring loaded down with trivial details subsequent processes, easily cause contamination of products, and while removing template agent removing, easily cause the fall damage of three dimensional structure, have a strong impact on products application and be worth；Solvent-thermal method is using organic solvent as reaction medium, and its boiling point is relatively low, and majority of organic solvent easily causes water pollution to human health, the waste water produced in last handling process.
Boron and compound thereof are rich in mineral resources and of many uses in China, and Borate Minerals is of a great variety, and the composition changeable due to it and special performance and potential application in various fields are of increased attention.Wherein Calcium pyroborate can extensively be applied as fire retardant, antiwear additive and optics host material.[Nd YCOB crystal micro lens self-doubled frequency green (light) laser, patent of invention, publication number: CN101237119A；A kind of preparation method of modified Nano Calcium pyroborate lube oil additive, patent of invention, publication number: CN103332701A；A kind of nano-stage calcium borate and application thereof, patent of invention, publication number: CN101239725A]；Recently, Huang Yanlin et al. finds that Calcium pyroborate can have preferable application prospect as a kind of excellent bioactive materials [a kind of Calcium borate biological material, preparation method and applications, patent of invention, publication number: CN103755325A].Oval 4CaO 5B is obtained with PEG-300 for synthesis of surfactant except the reports such as Liu Zhihong are a kind of for having the Calcium pyroborate nano material of specific three dimensional pattern2O3·7H2Outside O microsphere, synthesis and the application of the three-dimensional multistage material that other Calcium pyroborates are relevant still rarely have report.The invention provides a kind of hydration Calcium pyroborate (Ca4B10O19·7H2O) microsphere and anhydrous multistage porous Calcium pyroborate (Ca (BO2)2) low-temperature hydrothermal-thermal transition synthetic method, not only mild condition of microsphere, simple to operate, and without additional additive, during utilizing hydrothermal product subsequent calcination, water of crystallization removing prepares multistage loose structure.
This seminar have accumulated rich experiences before this [to orchid, Zhu Wancheng, Zhu Shenlin, the hydro-thermal synthetic preparation method of a kind of magnesium borate crystal whisker, Chinese patent ZL200610113032.8 in the synthesis of "Antifungin". monodimension nanometer material；Zhu Wancheng, Wang Ruguo, Zhu Shanlin, Zhang Linlin, Zhang Qiang, a kind of Green Water process for thermosynthesizing of atresia highly crystalline "Antifungin". nano whisker. patent of invention, publication number: CN103774208A], this seminar reports the ion process for thermosynthesizing [Zhu Wancheng of a kind of three-dimensional "Antifungin". superstructure recently, Zhang Zhaoqiang, Yu You, Wang Ruguo, Zhang Linlin, Zhu Lin, Zhang Qiang, a kind of microspheroidal porous alkali formula "Antifungin". and the ion process for thermosynthesizing of "Antifungin". nano-superstructure. patent of invention, publication number: CN104140112A].Based on seminar, certain effort [Shortbelt-like Ca is also made in boratory cognition, the synthesis to Calcium pyroborate simultaneously2B2O5·H2O
nanostructures: Hydrothermal formation, FT-IR, thermal decomposition, and
optical properties. Journal
of Crystal Growth , 2011, 332: 81–86. Hierarchical laminar superstructures of rhombic priceite (Ca4B10O19·7H2O):
Facile hydrothermal
synthesis, shape evolution, optical, and thermal decomposition properties. Cryst . Growth Des. 2011,
11:2935-2941].The present invention will expand the exploitation of China's boron resource further, and the synthesis for other class borate three-dimensional materials simultaneously is offered reference.
Summary of the invention
It is an object of the invention to provide a kind of low-temperature hydrothermal-thermal transition synthetic method being hydrated Calcium pyroborate microsphere and anhydrous multistage porous Calcium pyroborate microsphere, realize hydration Calcium pyroborate (Ca by the addition of mole when alkali of regulation raw materials of Ca and B4B10O19·7H2O) the controlled preparation of the hydro-thermal of microsphere, the medium temperature roast utilizing hydrothermal product follow-up realizes the removing of water of crystallization, and preparation degree of crystallinity is high, form the anhydrous multistage porous Calcium pyroborate (Ca (BO of three-dimensional pure, that distribution of sizes is homogeneous2)2) microsphere, have simple to operate, mild condition, cheaper starting materials are easy to get, need not the advantage such as any additive, it is easy to industrialized production.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, comprise the following steps:
(1) 2-10 ml aqueous slkali is added in 10 ml calcium salt solns, mix homogeneously, obtain mixed solution；
(2) control Ca/B mol ratio, borate pressed powder is added in mixed solution, add 10-20 ml water, stir 10-15
Min, obtains slip liquid；
(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 90-150
C, is cooled to room temperature after isothermal reaction 6.0-18.0 h, obtains hydrothermal product；
(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h at 70 DEG C, Calcium pyroborate (Ca must be hydrated4B10O19·7H2O) microsphere；
(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and certain heating rate is warming up to 650-750 DEG C, roasting 1.0-12.0
Naturally cool to room temperature after h, obtain crude product；
(6) crude product is sequentially passed through washing, filters, be dried 24.0 h at 70 DEG C, obtain anhydrous multistage porous Calcium pyroborate (Ca (BO2)2) micro-sphere material.
Described, it is hydrated Calcium pyroborate (Ca4B10O19·7H2O) in microsphere the diameter Distribution of 86.0-93.0 % at 0.5-5.0
μm, described, anhydrous multistage porous Calcium pyroborate (Ca (BO2)2) in microsphere the diameter Distribution of 89.0-96.0 % at 1.0-6.0
μm。
Described, Ca/B mol ratio is 1:2-4.
Described, calcium salt is calcium chloride or calcium nitrate, described, and the concentration of calcium salt soln is 0.5-0.8 mol/L.
Described, borate is boric acid or Borax.
Described, aqueous slkali is the one in ammonia, urea liquid, ethylenediamine, hydroxylamine hydrochloride solution.
Described, the concentration of urea liquid is 0.5 mol/L, described, and the concentration of hydroxylamine hydrochloride solution is 0.4 mol/L.
Described, heating rate is 1-10 C/min.
The mass concentration of ammonia used by the present invention is 28.0 %, and the mass concentration of ethylenediamine is 99.0 %, and wherein ammonia, ethylenediamine are commercially available.
Beneficial effects of the present invention:
Mild condition the most of the present invention, first passes through the addition of mole when alkali of regulation raw materials of Ca and B, it is achieved that Ca4B10O19·7H2The controlled preparation of hydro-thermal of O microsphere, utilizes water evaporation in roasting process to define Ca (BO afterwards2)2Multistage loose structure, and preferably keep product morphology, final prepared degree of crystallinity is high, form anhydrous multistage porous C a (BO pure, that distribution of sizes is more uniform2)2Microsphere.
2. the present invention need not any additive, it is to avoid add template in conventional three-dimensional material synthesis processes or loaded down with trivial details post processor that derivant causes and pollution, prepared Ca4B10O19·7H2O microsphere and multistage porous C a (BO2)2Microsphere composition is pure.
3. the cheaper starting materials of the present invention is easy to get, simple to operate, mild condition, energy consumption are low, and suitable large-scale industry is promoted.
Accompanying drawing explanation
Fig. 1 is Ca in embodiment 24B10O19·7H2Multistage porous C a (BO in O microsphere and embodiment 42)2The XRD figure spectrum of microsphere；
Fig. 2 is Ca in embodiment 24B10O19·7H2The SEM figure of O microsphere；
Fig. 3 is Ca in embodiment 34B10O19·7H2The SEM figure of O microsphere；
Fig. 4 is multistage porous C a (BO in embodiment 42)2The SEM figure of microsphere；
Fig. 5 is multistage porous C a (BO in embodiment 52)2The SEM figure of microsphere.
Detailed description of the invention
Below by specific embodiment, the invention will be further described.
Embodiment
1
A kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, comprise the following steps: the ammonia of 10 ml is added in the calcium chloride solution of 10 ml 0.5 mol/L by (1), and mix homogeneously obtains mixed solution；(2) 0.005 mol Borax pressed powder is added in mixed solution, add 20 ml water, stir 10 min, obtain slip liquid；(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 120 C, naturally cools to room temperature after isothermal reaction 9.0 h, obtain hydrothermal product；(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h under 70 C, obtain Ca4B10O19·7H2O microsphere；(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and 5 C/min heating rates are warming up to 650 C, naturally cool to room temperature, obtain crude product after roasting 12.0 h；(6) crude product is sequentially passed through washing, filters, be dried 24.0 h under 70 C, obtain multistage porous C a (BO2)2Microsphere.
The Ca that the present embodiment prepares4B10O19·7H2In O microsphere, the diameter Distribution of 90.0% is at 1.0-5.0 μm, multistage porous C a (BO2)2In microsphere, the diameter Distribution of 95.3 % is in 2.0-6.0 μm.
Embodiment
2
A kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, comprise the following steps: 2 ml ethylenediamines are added in the calcium chloride solution of 10 ml 0.8 mol/L by (1), and mix homogeneously obtains mixed solution；(2) the Borax pressed powder of 0.005 mol is added in mixed solution, add 20 ml water, stir 10 min, obtain slip liquid；(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 100 C, naturally cools to room temperature after isothermal reaction 12.0 h, obtain hydrothermal product；(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h under 70 C, obtain Ca4B10O19·7H2O microsphere；(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and 5 C/min heating rates are warming up to 750 C, naturally cool to room temperature, obtain crude product after roasting 2.0 h；(6) crude product is sequentially passed through washing, filters, be dried 24.0 h under 70 C, obtain multistage porous C a (BO2)2Microsphere.
The Ca that the present embodiment prepares4B10O19·7H2In O microsphere, the diameter Distribution of 93.0 % is at 0.5-4.0 μm, multistage porous C a (BO2)2In microsphere, the diameter Distribution of 89.0 % is in 1.0-6.0 μm.
As seen from Figure 1, Ca4B10O19·7H2The XRD figure of O microsphere is coincide with XRD standard card JCPDS No.09-0147 data；As seen from Figure 2, Ca4B10O19·7H2O presents microspheroidal pattern, and surface is more smooth, microsphere diameter 0.5-4.0 μm.
Embodiment
3
A kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, comprise the following steps: (1) is by 10 ml
The hydroxylamine hydrochloride solution of 0.4 mol/L adds in the calcium chloride solution of 10 ml 0.8 mol/L, and mix homogeneously obtains mixed solution；(2) 0.016mol boric acid pressed powder is added in mixed solution, add 10 ml water, stir 10
Min, obtains slip liquid；(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 150 C, is cooled to room temperature after isothermal reaction 6.0 h, obtains hydrothermal product；(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h under 70 C, obtain Ca4B10O19·7H2O microsphere；(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and 10 C/min heating rates are warming up to 650 C, naturally cool to room temperature, obtain crude product after roasting 2.0 h；(6) crude product is sequentially passed through washing, filters, be dried 24.0 h under 70 C, obtain anhydrous multistage porous C a (BO2)2Microsphere.
The Ca that the present embodiment prepares4B10O19·7H2In O microsphere, the diameter Distribution of 90.0% is at 1.0-4.5 μm, multistage porous C a (BO2)2In microsphere, the diameter Distribution of 92.4 % is in 1.0-5.0 μm.
As seen from Figure 3, Ca4B10O19·7H2O presents smooth microsphere pattern, and microsphere diameter relatively concentrates near 2.0 μm.
Embodiment
4
A kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, comprise the following steps: (1) is by 10 ml
The urea liquid of 0.5 mol/L adds in the calcium nitrate solution of 10 ml 0.8 mol/L, and mix homogeneously obtains mixed solution；(2) by 0.005
Mol Borax pressed powder adds in mixed solution, adds 20 ml water, stirs 10 min, obtains slip liquid；(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 90 C, is cooled to room temperature after isothermal reaction 18.0 h, obtains hydrothermal product；(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h under 70 C, obtain Ca4B10O19·7H2O microsphere；(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and 5 C/min heating rates are warming up to 700 C, naturally cool to room temperature, obtain crude product after roasting 2.0 h；(6) crude product is sequentially passed through washing, filters, be dried 24.0 h under 70 C, obtain anhydrous multistage porous C a (BO2)2Microsphere.
The Ca that the present embodiment prepares4B10O19·7H2In O microsphere, the diameter Distribution of 92.0% is in 0.5-4.5 μm, anhydrous multistage porous C a (BO2)2In microsphere, the diameter Distribution of 91.0 % is in 1.5-5.0 μm.
As seen from Figure 1, anhydrous multistage porous C a (BO2)2The XRD figure of microsphere is coincide with XRD standard card JCPDS No.78-1277 data；As seen from Figure 4, multistage porous C a (BO2)2Microsphere pattern keeps good, and the most internal have more pore structure, and diameter dimension concentrates on 1.5-5.0 μm.
Embodiment
5
A kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, comprise the following steps: 10 ml ammonia are added in the calcium nitrate solution of 10 ml 0.5 mol/L by (1), and mix homogeneously obtains mixed solution；(2) 0.01 mol boric acid pressed powder is added in mixed solution, add 20 ml water, stir 15 min, obtain slip liquid；(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 100 C, is cooled to room temperature after isothermal reaction 12.0 h, obtains hydrothermal product；(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h under 70 C, obtain Ca4B10O19·7H2O microsphere；(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and 1 C/min heating rate is warming up to 650 C, naturally cools to room temperature, obtain crude product after roasting 2.0 h；(6) crude product is sequentially passed through washing, filters, be dried 24.0 h under 70 C, obtain anhydrous multistage porous C a (BO2)2Microsphere.
The Ca that the present embodiment prepares4B10O19·7H2In O microsphere, the diameter Distribution of 87.0 % is at 1.0-5. 0 μm, multistage porous C a (BO2)2In microsphere, the diameter Distribution of 89.0% is in 2.0-6.0 μm.
From fig. 5, it can be seen that multistage porous C a (BO2)2The pattern of microsphere keeps preferably, more ball due in heating process the removing of water of crystallization and Decrepitation Phenomena occurs so that the acute pore structure having complexity in calcination product, final calcination product diameter Distribution is in 2.0-6.0
About μm.
Embodiment
6
A kind of hydration and the low-temperature hydrothermal-thermal transition synthetic method of anhydrous multistage porous Calcium pyroborate microsphere, comprise the following steps: 3 ml ethylenediamines are added in the calcium nitrate solution of 10 ml 0.8 mol/L by (1), and mix homogeneously obtains mixed solution；(2) 0.006 mol Borax pressed powder is added in mixed solution, add 10 ml water, stir 10 min, obtain slip liquid；(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 90 C, is cooled to room temperature after isothermal reaction 18.0 h, obtains hydrothermal product；(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h under 70 C, obtain Ca4B10O19·7H2O microsphere；(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and 10 C/min heating rates are warming up to 750 C, naturally cool to room temperature, obtain crude product after roasting 1.0 h；(6) crude product is sequentially passed through washing, filters, be dried 24.0 h under 70 C, obtain multistage porous C a (BO2)2Microsphere.
The Ca that the present embodiment prepares4B10O19·7H2In O microsphere, the diameter Distribution of 90.0 % is at 0.4-4.0 μm, multistage porous C a (BO2)2In microsphere, the diameter Distribution of 93.5 % is in 1.0-5.5 μm.
Claims (5)
1. low-temperature hydrothermal-thermal transition the synthetic method of an anhydrous multistage porous Calcium pyroborate microsphere, it is characterised in that comprise the following steps:
(1) 2-10ml aqueous slkali is added in 10ml calcium salt soln, mix homogeneously, obtain mixed solution；
Described aqueous slkali is the one in ammonia, urea liquid, ethylenediamine, hydroxylamine hydrochloride solution；
(2) control Ca/B mol ratio, the pressed powder of boric acid or Borax is added in mixed solution, add 10-20ml water, stir 10-15 min, obtain slip liquid；
(3) slip liquid is placed in hydrothermal reaction kettle, is warming up to 90-150 C, is cooled to room temperature after isothermal reaction 6.0-18.0h, obtains hydrothermal product；
(4) hydrothermal product is sequentially passed through washing, filters, be dried 12.0 h under 70 C, Calcium pyroborate Ca must be hydrated4B10O19·7H2O microsphere；
(5) by Ca4B10O19·7H2O microsphere is placed in roaster, and certain heating rate is warming up to 650-750 DEG C, naturally cools to room temperature, obtain crude product after roasting 1.0-12.0h；
(6) crude product is sequentially passed through washing, filters, be dried 24.0 h under 70 C, obtain anhydrous multistage porous Calcium pyroborate Ca (BO2)2Microsphere；Described Ca4B10O19·7H2In O microsphere, the diameter Distribution of 86.0-93.0% is in 0.5-5.0 μm, described multistage porous C a (BO2)2In microsphere, the diameter Distribution of 89.0-96.0% is in 1.0-6.0 μm.
Synthetic method the most according to claim 1, it is characterised in that described Ca/B mol ratio is 1:2-4.
Synthetic method the most according to claim 1, it is characterised in that described calcium salt is calcium chloride or calcium nitrate, the concentration of described calcium salt soln is 0.5-0.8mol/L.
Synthetic method the most according to claim 1, it is characterised in that the concentration of described urea liquid is 0.5mol/L, the concentration of described hydroxylamine hydrochloride solution is 0.4mol/L.
Synthetic method the most according to claim 1, it is characterised in that described heating rate is 1-10 C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510198818.3A CN104817094B (en) | 2015-04-24 | 2015-04-24 | Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510198818.3A CN104817094B (en) | 2015-04-24 | 2015-04-24 | Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104817094A CN104817094A (en) | 2015-08-05 |
| CN104817094B true CN104817094B (en) | 2017-01-11 |
Family
ID=53727606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510198818.3A Expired - Fee Related CN104817094B (en) | 2015-04-24 | 2015-04-24 | Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104817094B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082252B (en) * | 2016-05-28 | 2018-05-25 | 曲阜师范大学 | A kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084137A (en) * | 1992-09-17 | 1994-03-23 | 雷振玺 | The method that from boron rock, prepares lime borate |
-
2015
- 2015-04-24 CN CN201510198818.3A patent/CN104817094B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084137A (en) * | 1992-09-17 | 1994-03-23 | 雷振玺 | The method that from boron rock, prepares lime borate |
Non-Patent Citations (1)
| Title |
|---|
| 水热法合成硼酸钙的工艺研究与性能表征;曹惠峰;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20080315(第3期);第19-20、31、40页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104817094A (en) | 2015-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103466702B (en) | Method for preparing porous bismuth oxide nano-material without template | |
| CN102757075B (en) | Method for preparing calcium carbonate powders of different structures and shapes | |
| CN107500303B (en) | A kind of mesoporous magnesium silicate microballoon and its hydro-thermal-thermal transition preparation method | |
| CN102329613A (en) | Hydro-thermal preparation method for spherical boric acid yttrium doped europium fluorescent powder in hollow structure | |
| CN104790024A (en) | Preparation method for aragonite calcium carbonate whisker with high length-diameter ratio | |
| CN110272058B (en) | MCM-41 ordered mesoporous material and preparation method thereof | |
| CN102936019A (en) | Method for preparing magnetic 4A molecular sieve by using kaolin | |
| CN102303906B (en) | Ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4 | |
| CN109734056A (en) | Metal oxide/preparation method of fold rGO composite nano materials and the preparation method of fold nano-metal-oxide | |
| CN101311372B (en) | Low-temperature molten salt thermal inversion preparation method of aporate-crystal antifungin whiskers | |
| CN101531375A (en) | Method for synthesizing bimodal silicon-aluminum mesoporous material | |
| CN107804854A (en) | The method that cupric silicate nanotube is prepared using low-grade attapulgite clay | |
| Si et al. | Simultaneous removal of nitrogen and phosphorus by magnesium-modified calcium silicate core-shell material in water | |
| CN104817094B (en) | Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method | |
| CN105821476A (en) | Mild hydrothermal-thermal transition synthetic method for high-draw-ratio hydrated and anhydrous calcium borate nanowhisker | |
| CN103253679A (en) | Method of synthesizing SBA-15 mesoporous molecular sieve | |
| CN109019618A (en) | A kind of preparation method of cupric silicate hollow microsphere | |
| CN103601210B (en) | Wilkinite one step alkali is fused into the method for zeolite | |
| CN106564873B (en) | A kind of big micro-diplopore film carbon material and preparation method thereof | |
| CN106517271A (en) | Preparation method of magnesium-aluminum hydrotalcite nanosheet | |
| CN106830024B (en) | A kind of red mud prepares hydro-thermal-thermal conversion process of active boehmite and aluminum oxide porous microballoon for raw material | |
| CN101555042A (en) | Method for preparing spinel type iron-containing oxide nano-materials by low heat solid state reaction | |
| Demirkiran et al. | Dissolution of thermally dehydrated ulexite in ammonium acetate solutions | |
| CN103922385B (en) | A kind of preparation method of cerium oxide hexagonal nanosheet shape structure | |
| CN103833080A (en) | Preparation method for cadmium molybdate porous spheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170111 |