CN106082252A - A kind of hydration Calcium pyroborate microsphere, anhydrous boric acid calcium microsphere and preparation method thereof - Google Patents
A kind of hydration Calcium pyroborate microsphere, anhydrous boric acid calcium microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN106082252A CN106082252A CN201610369590.4A CN201610369590A CN106082252A CN 106082252 A CN106082252 A CN 106082252A CN 201610369590 A CN201610369590 A CN 201610369590A CN 106082252 A CN106082252 A CN 106082252A
- Authority
- CN
- China
- Prior art keywords
- microsphere
- calcium
- preparation
- present
- hydro
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/126—Borates of alkaline-earth metals, beryllium, aluminium or magnesium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides a kind of hydration Calcium pyroborate microsphere and anhydrous boric acid calcium microsphere and preparation method thereof.The present invention uses hydro-thermal thermal conversion process, with calcium salt, boron source and alkali source as raw material, by adding surfactant in aqueous, Effective Regulation product composition and pattern, the hydration Calcium pyroborate microsphere of size uniformity is obtained through hydro-thermal reaction, the most fired raising degree of crystallinity, obtains the anhydrous boric acid calcium microsphere of size uniformity, is expected to be used widely containing heavy metal ion or dye wastewater treatment, supported catalyst, the field such as fire-retardant.The preparation method that the present invention provides is simple to operate, mild condition, energy consumption are low, with low cost, technique is easily-controllable, and suitable large-scale industry is promoted.
Description
Technical field
The present invention relates to technical field of inorganic chemical industry, be hydrated Calcium pyroborate microsphere, anhydrous boric acid calcium microsphere particularly to one
And preparation method thereof.
Background technology
In recent years, three-dimensional multistage structure nano material is due to excellent performance, and structure is unique, and specific surface area is high, mechanical strength
The advantage such as good and receive much concern, and be widely used in energy storage, sensor, the fields such as water processes, catalyst carrier.Due to boron
The composition that hydrochlorate is changeable and the special performance in various fields and potential application thereof receive more and more concern.Wherein, boron
Acid calcium is widely used as fire retardant, it is also possible to for industry such as Chinese white, pottery, glass, papermaking, rubber and plastics.Synthesis
The cost of Calcium pyroborate is equivalent to 1.3 times of boric acid price, is the fire retardant that cost is minimum, and has the boric acid of three-dimensional multistage structure
Calcium more becomes study hotspot.
At present, the Calcium pyroborate of three-dimensional multistage structure mainly utilizes hydro-thermal method, solvent-thermal method and solid reaction process synthesis to obtain.
Solvent-thermal method, using organic solvent as reaction medium, has certain help to the regulation and control of three-dimensional appearance, but majority of organic solvent pair
Human health, the waste water produced in last handling process easily causes water pollution；Solid reaction process compares other method gained
Product heat stability is high, but severe reaction conditions, energy consumption is big, and product morphology heterogeneity.Therefore, comparatively speaking, hydro-thermal method
It it is a kind of method of synthesis three-dimensional multistage structure Calcium pyroborate being widely used.
Zhu, W.C. etc. report a kind of multistage hydration Calcium pyroborate (Ca assembled by losenges4B10O19·7H2O) super
Structure (Zhu, W.C.；Wang,X.L.et al.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.), but this product size is relatively big, and owing to losenges is weak with the Interaction Force of sheet, causes product pellet stability inclined
Difference, is susceptible to de-assembly, it is impossible to fired process obtains anhydrous boric acid calcium；The Chinese patent of Publication No. CN104817094A
Also disclose that a kind of by hydro-thermal-thermal transition preparation hydration and the method for anhydrous multistage porous Calcium pyroborate microsphere, but the said goods
Particle morphology homogeneity is poor, and microsphere surface relative smooth is fine and close, and pore structure is the abundantest, and microsphere size is uneven, diameter Distribution
Wide in range.
Summary of the invention
It is an object of the invention to provide a kind of hydration Calcium pyroborate microsphere, anhydrous boric acid calcium microsphere and preparation method thereof, purport
A kind of Heat stability is good is being provided, there is the hydration Calcium pyroborate microsphere of hierarchical porous structure and size uniform, anhydrous boric acid calcium microsphere
And preparation method thereof.
The invention provides a kind of preparation method being hydrated Calcium pyroborate microsphere, comprise the following steps:
(1) calcium salt, alkali source and water are mixed, obtain mixed serum；
(2) mixed serum that described step (1) obtains is mixed with surfactant, obtain mixed solution；
(3) being mixed with boron source by the mixed solution that described step (2) obtains, hydro-thermal reaction obtains being hydrated Calcium pyroborate microsphere.
Preferably, Ca in described step (1) calcium salt2+It is 1:2～4 with the mol ratio of OH-in alkali source.
Preferably, in described step (2), the mole of surfactant is Ca in described calcium salt2+Mole 1.6～
50%.
Preferably, described surfactant is citric acid, sodium citrate, disodiumedetate and ethylenediaminetetraacetic acid
In one or more.
Preferably, the B in boron source and Ca in described calcium salt in described step (3)2+Mol ratio be 1:2～4.
Preferably, in described step (3), the temperature of hydro-thermal reaction is 150～210 DEG C, the pressure of hydro-thermal reaction be 0.12～
0.23MPa, the time of hydro-thermal reaction is 1～24h.
Present invention also offers hydration Calcium pyroborate microsphere prepared by preparation method described in technique scheme, by nanometer sheet group
Dress forms, and the particle diameter of described microsphere is 6～15 μm.
Present invention also offers the preparation method of a kind of anhydrous boric acid calcium microsphere, boric acid will be hydrated described in technique scheme
Calcium microsphere carries out roasting, obtains anhydrous boric acid calcium microsphere.
Preferably, the temperature of described roasting is 650～750 DEG C, and the time of described roasting is 1～12h.
Anhydrous boric acid calcium microsphere prepared by the method described in technique scheme that present invention also offers, the particle diameter of described microsphere
It is 9～16 μm.
The present invention uses hydro-thermal-thermal conversion process, with calcium salt, boron source and alkali source as raw material, by adding in aqueous
Surfactant, Effective Regulation product composition and pattern, the hydration Calcium pyroborate microsphere of size uniformity, then warp is obtained through hydro-thermal reaction
Roasting improves degree of crystallinity, obtains the anhydrous boric acid calcium microsphere of size uniformity, be expected to containing heavy metal ion or dye wastewater treatment,
Are used widely in supported catalyst, the field such as fire-retardant.Test result indicate that, the hydration boron that the method that the present invention provides prepares
Acid calcium microsphere and anhydrous boric acid calcium microsphere are and have hierarchical porous structure, Heat stability is good, uniform particle sizes, are hydrated Calcium pyroborate microsphere
Particle diameter be 6～15 μm, the particle diameter of described anhydrous boric acid calcium microsphere is 9～16 μm.
The preparation method that the present invention provides is simple to operate, mild condition, energy consumption are low, with low cost, technique is easily-controllable, the most greatly
Technical scale is promoted.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the hydration Calcium pyroborate microsphere obtained in embodiment 1；
Fig. 2 is the SEM image of the hydration Calcium pyroborate microsphere obtained in embodiment 1；
Fig. 3 is the XRD figure spectrum of the anhydrous boric acid calcium microsphere obtained in embodiment 2；
Fig. 4 is the SEM image of the hydration Calcium pyroborate microsphere obtained in embodiment 3；
Fig. 5 is the SEM image of the anhydrous boric acid calcium microsphere obtained in embodiment 6.
Detailed description of the invention
The invention provides a kind of preparation method being hydrated Calcium pyroborate microsphere, comprise the following steps:
(1) calcium salt, alkali source and water are mixed, obtain mixed serum；
(2) mixed serum that described step (1) obtains is mixed with surfactant, obtain mixed solution；
(3) being mixed with boron source by the mixed solution that described step (2) obtains, hydro-thermal reaction obtains being hydrated Calcium pyroborate microsphere.
Calcium salt, alkali source and water are mixed by the present invention, obtain mixed serum.The present invention is the most special to the operation of described mixing
Restriction, use the method preparing mixed serum well known to those skilled in the art.The present invention is preferably by calcium salt with water first
Mix, obtain calcium salt soln；Again described calcium salt soln is mixed with alkali, obtain mixed serum.In the present invention, described mixed
Close and carry out the most under agitation.In the present invention, described stirring is preferably magnetic agitation；The speed of described stirring is preferably
350～450rpm/min；The time of described stirring is preferably 5～10min.In the present invention, Ca in described calcium salt soln2+Rub
You are preferably 0.5～2mol/L at concentration, more preferably 1～1.5mol/L.
For making calcium salt fully react with alkali source, it is molten that described alkali source is preferably added drop-wise to described calcium salt by the present invention in the form of a solution
Liquid is carried out be mixed to get mixed serum.In the present invention, the molar concentration of described alkali source solution is preferably 1～8mol/L, more
It is preferably 3～5mol/L.In the present invention, the speed of described dropping is preferably 2.5～3.5mL/min.In the present invention, described
Mixing is carried out the most under agitation.In the present invention, described stirring is preferably magnetic agitation；The speed of described stirring is preferred
It is 350～450rpm/min；The time of described stirring is preferably 10～15min.
In the present invention, described calcium salt is preferably soluble calcium salt, more preferably in calcium nitrate, calcium chloride and calcium acetate
One or more.In the present invention, the most isolated and purified, improve product purity, described calcium salt be most preferably calcium nitrate,
One in calcium chloride and calcium acetate.The present invention does not has special restriction to the kind of described alkali source, uses people in the art
Alkali source known to Yuan.Dangerous big, the environmental pollution that exist in order to avoid organic base greatly and amplify the defects such as difficulty, at this
In invention, described alkali source is preferably inorganic alkali source, more preferably inorganic soluble alkali source, concrete Wei solubility hydroxide
Thing, most preferably potassium hydroxide and/or sodium hydroxide；The most isolated and purified, improve the purity of product, described alkali source is optimum
Elect potassium hydroxide or sodium hydroxide as.In the present invention, described water is preferably deionized water.
In the present invention, Ca in described calcium salt2+With OH in described alkali source-Mol ratio be preferably 1:2～4, more preferably
1:2.5～3.5.
After obtaining mixed serum, described mixed serum is mixed by the present invention with surfactant, obtains mixed solution.At this
In invention, the mole of described surfactant is preferably Ca in described calcium salt2+The 1.6～50% of mole, more preferably 10
～30%, most preferably 20～25%.In the present invention, described surfactant is preferably citric acid, sodium citrate, ethylenediamine
One or more in tetraacethyl disodium and ethylenediaminetetraacetic acid；The most isolated and purified, improve the purity of product, described table
Face activating agent is more preferably the one in citric acid, sodium citrate, disodiumedetate and ethylenediaminetetraacetic acid.
Described surfactant is preferably added in mixed serum by the present invention, and stirring obtains mixed solution.In the present invention,
Described surfactant can be with Ca in solution2+Reaction forms chelate, reduces Free Ca in solution2+Concentration, thus control to produce
Thing slowly generates, and promotes nanometer sheet oriented growth and self assembly generation size is less and uniform, the uniform microsphere of pattern.At this
In bright, described stirring is preferably magnetic agitation；The speed of described stirring is preferably 350～450rpm/min；Described stirring time
Between be preferably 10～20min, more preferably 14～16min.
After obtaining mixed solution, described mixed solution is mixed by the present invention with boron source, and hydro-thermal reaction obtains being hydrated Calcium pyroborate.
In the present invention, B and Ca in described calcium salt in described boron source2+Mol ratio be preferably 1:2～4, more preferably 1:2.5～3.5.
In the present invention, described boron source is preferably boric acid and/or Borax, the most isolated and purified, improves the purity of product, described boron
Source is more preferably boric acid or Borax.
For making reactant more fully mix, promoting particle form more uniform, the present invention is preferably by described boron
Source is added drop-wise in described mixed solution carry out being mixed to get hydro-thermal presoma in the form of a solution.In the present invention, described boron source is molten
Liquid is preferably the aqueous solution of boron source；The molar concentration of described boron source solution be preferably 0.2～0.8mol/L, more preferably 0.3～
0.6mol/L.In the present invention, the speed of described dropping is preferably 2.5～3.5mL/min.In the present invention, described mixing is excellent
Choosing is carried out under agitation.In the present invention, described stirring is preferably magnetic agitation；The speed of described stirring is preferably 350
～450rpm/min；The time of described stirring is preferably 10～20min, more preferably 14～16min.
After obtaining hydro-thermal presoma, described hydro-thermal presoma is carried out hydro-thermal reaction by the present invention, obtains being hydrated Calcium pyroborate micro-
Ball.The present invention does not has special restriction to the device of described hydro-thermal reaction, uses hydro-thermal reaction well known to those skilled in the art
Device.In the present invention, described hydro-thermal reaction is preferably carried out in hydrothermal reaction kettle.In the present invention, described hydro-thermal
The temperature of reaction is preferably 150～210 DEG C, more preferably 170～190 DEG C, most preferably 175～185 DEG C；The pressure of hydro-thermal reaction
Power is preferably 0.12～0.23MPa, more preferably 0.15～0.21MPa；The present invention is preferably at a temperature of described hydro-thermal reaction
Insulation carries out hydro-thermal reaction, and the time of described insulation is preferably 1～24h, more preferably 5～18h, most preferably 10～12h.
In the present invention, be warming up to the speed of described hydrothermal temperature and be preferably 5～15 DEG C/min, more preferably 8～
12℃/min.In the present invention, described reaction temperature can become phase velocity, by ripe from aerodynamic point regulation and control product with the time
Change mechanism improving product particle crystallization degree to avoid again excessive temperature simultaneously, obtain size uniform after the undue growth caused for a long time
Product.
In order to improve the purity of product, the present invention preferably product to described hydro-thermal reaction washs, filters and is dried.
The present invention does not has special restriction to the operation of described washing and filtration, uses washing well known to those skilled in the art, filtration
With dry operation.In the present invention, the detergent that described washing is used is preferably deionized water and ethanol.In the present invention
Preferably the hydration Calcium pyroborate microsphere obtained respectively is washed 3～5 times through deionized water and ethanol successively.In the present invention, described mistake
Filter is preferably sucking filtration；The device of described sucking filtration is preferably buchner funnel.In the present invention, described dry temperature be preferably 70～
100 DEG C, more preferably 80～90 DEG C, most preferably 84～88 DEG C；The described dry time is preferably 12～24h, more preferably
16～20h, most preferably 17～19h.
Present invention also offers hydration Calcium pyroborate microsphere prepared by preparation method described in technique scheme, by nanometer sheet group
Dress forms, and the particle diameter of described microsphere is that 6～15 μm are more preferably 7～12 μm.In the present invention, the shape of described nanometer sheet is preferred
For hexagon, the thickness of described nanometer sheet is preferably 70～90nm, more preferably 75～85nm.
Present invention also offers the preparation method of a kind of anhydrous boric acid calcium microsphere, boric acid will be hydrated described in technique scheme
Calcium microsphere carries out roasting, obtains anhydrous boric acid calcium microsphere.The present invention does not has special restriction to the device of described roasting, uses this
The device of the roasting known to skilled person.In the present invention, described roasting is preferably carried out in tube furnace.At this
In bright, the temperature of described roasting is preferably 650～750 DEG C, more preferably 680～720 DEG C, most preferably 690～710 DEG C；?
Under described sintering temperature, the time of roasting is preferably 1～12h, more preferably 4～10h, most preferably 6～8h.In the present invention,
The described speed being warming up to sintering temperature is preferably 1～10 DEG C/min, more preferably 4～6 DEG C/min.In the present invention, described
Roasting can realize Ca4B10O19·7H2O to Ca (BO2)2Phase in version, improve anhydrous Ca (BO simultaneously2)2The degree of crystallinity of microsphere.
Anhydrous boric acid calcium microsphere prepared by the method described in technique scheme that present invention also offers, the particle diameter of described microsphere
It is 9～16 μm, more preferably 12～14 μm.
In order to further illustrate the present invention, the hydration Calcium pyroborate microsphere that the present invention provided below in conjunction with embodiment and anhydrous
The preparation method of Calcium pyroborate microsphere is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1:
(1) addition of 10mL deionized water is filled in 5mmol calcium nitrate solid beaker, rotating speed 400rpm/min magnetic agitation
Mixed liquor is obtained after 10min；
(2) by 10mL 1mol L-1KOH solution drops in mixed solution, rate of addition 3mL/min, continues rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) being joined in (2) gained mixed solution by 0.3125mmol EDTA-2Na solid, rotating speed 400rpm/min stirs
Mix 5min；
(4) 30mL is contained the H of 20mmol3BO3Solution is added dropwise to (3) gained mixed solution, rate of addition 3mL/min, continues
Continuous rotating speed 400rpm/min stirs 15min, obtains hydro-thermal presoma；
(5) hydro-thermal presoma is transferred in hydrothermal reaction kettle, is warming up to 210 DEG C with 10 DEG C/min heating rate, constant temperature
Naturally cool to room temperature after 1.0h and obtain hydrothermal product；
(6) hydrothermal product sequentially passes through deionized water and dehydrated alcohol respectively washs three times, uses buchner funnel sucking filtration, does for 70 DEG C
Dry 12.0h, obtains Ca4B10O19·7H2O microsphere.
The Ca that the present embodiment prepares4B10O19·7H2The XRD figure of O microsphere is composed as shown in Figure 1.It can be seen that
Ca4B10O19·7H2The XRD figure of O microsphere is mated preferably with XRD standard card JCPDS No.10-0463, illustrates that product forms relatively
Pure.
The Ca that the present embodiment prepares4B10O19·7H2The SEM image of O microsphere is as shown in Figure 2.It can be seen that
Ca4B10O19·7H2O microsphere is assembled by the two-dimensional nano sheet of a size of 75nm, has hierarchical porous structure, and particle diameter is at 7～12 μ
M, even particle size distribution.
Embodiment 2:
Hydration Calcium pyroborate (the Ca that embodiment 1 is obtained4B10O19·7H2O) during microsphere is placed in tube furnace, with 10 DEG C/min liter
Temperature ramp, to 750 DEG C, naturally cools to room temperature after roasting 1.0h, obtains Ca (BO2)2Microsphere.
Ca (the BO that the present embodiment prepares2)2Microsphere XRD figure is composed as shown in Figure 3.It can be seen that Ca (BO2)2
The XRD figure of microsphere is mated preferably with XRD standard card JCPDS No.78-1277, and has extraordinary degree of crystallinity.
Ca (the BO that the present embodiment prepares2)2Microsphere has hierarchical porous structure, and particle diameter is in 9～14 μm, and particle diameter distribution is all
Even.
Embodiment 3:
(1) 10mL deionized water is added in the beaker filling 10mmol calcium chloride solid, rotating speed 400rpm/min magnetic force
Mixed liquor is obtained after stirring 10min；
(2) by 10mL 2mol L-1NaOH solution drop in mixed solution, rate of addition 3mL/min, continue rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) joining in (2) gained mixed solution by 2.5mmol EDTA solid, rotating speed 400rpm/min stirs 5min；
(4) 30mL is contained the H of 20mmol3BO3Solution is added dropwise to (3) gained mixed solution, rate of addition 3mL/min, continues
Continuous rotating speed 400rpm/min stirs 15min, obtains hydro-thermal presoma；
(5) will transfer in hydrothermal reaction kettle, be warming up to 180 DEG C with 10 DEG C/min heating rate, natural after constant temperature 12.0h
It is cooled to room temperature and obtains hydrothermal product；
(6) hydrothermal product sequentially passes through deionized water and dehydrated alcohol respectively washs three times, 70 DEG C of dry 12.0h,
Ca4B10O19·7H2O microsphere.
The Ca that the present embodiment prepares4B10O19·7H2The SEM image of O microsphere is as shown in Figure 4.It can be seen that
Ca4B10O19·7H2O microsphere is assembled by two-dimensional nano sheet, has hierarchical porous structure, and particle diameter is in 8～14 μm, and particle diameter distribution is all
Even.
Embodiment 4:
Hydration Calcium pyroborate (the Ca that embodiment 3 is obtained4B10O19·7H2O) during microsphere is placed in tube furnace, with 1 DEG C/min liter
Temperature ramp, to 650 DEG C, naturally cools to room temperature after roasting 12.0h, obtains Ca (BO2)2Microsphere.
Ca (the BO that the present embodiment prepares2)2Microsphere has hierarchical porous structure, and particle diameter is in 10～15 μm, and particle diameter distribution is all
Even.
Embodiment 5:
(1) 10mL deionized water is added in the beaker filling 20mmol calcium acetate solid, rotating speed 400rpm/min magnetic force
Mixed liquor is obtained after stirring 10min；
(2) KOH solution of 10mL 4mol L-1 is dropped in mixed solution, rate of addition 3mL/min, continues rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) joining in (2) gained mixed solution by 0.625mmol sodium citrate solid, rotating speed 400rpm/min stirs
5min；
(4) borax soln that 30mL is contained 10mmol is added dropwise to (3) gained mixed solution, rate of addition 3mL/min, continues
Continuous rotating speed 400rpm/min stirs 15min, obtains hydro-thermal presoma；
(5) hydro-thermal presoma is transferred in hydrothermal reaction kettle, is warming up to 150 DEG C with 9 DEG C/min heating rate, constant temperature
Naturally cool to room temperature after 24.0h and obtain hydrothermal product；
(6) hydrothermal product sequentially passes through deionized water and dehydrated alcohol respectively washs three times, 70 DEG C of dry 12.0h,
Ca4B10O19·7H2O microsphere.
The Ca that the present embodiment prepares4B10O19·7H2O microsphere is assembled by two-dimensional nano sheet, has multi-stage porous knot
Structure, particle diameter is in 8～14 μm, even particle size distribution.
Embodiment 6:
Hydration Calcium pyroborate (the Ca that embodiment 5 is obtained4B10O19·7H2O) during microsphere is placed in tube furnace, with 2.5 DEG C/min
Heating rate is warming up to 700 DEG C, naturally cools to room temperature after roasting 3.0h, obtains Ca (BO2)2Microsphere.
Ca (the BO that the present embodiment prepares2)2The SEM image of microsphere is as shown in Figure 5.It can be seen that Ca
(BO2)2Microsphere has hierarchical porous structure, and particle diameter is in 9～16 μm, even particle size distribution.
Embodiment 7:
(1) 10mL deionized water is added in the beaker filling 10mmol calcium chloride solid, rotating speed 400rpm/min magnetic force
Mixed liquor is obtained after stirring 10min；
(2) by 10mL 2mol L-1NaOH solution drop in mixed solution, rate of addition 3mL/min, continue rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) being joined by 1.25mmol citric acid solid in (2) gained mixed solution, rotating speed 400rpm/min stirs
5min；
(4) borax soln that 30mL is contained 10mmol is added dropwise to (3) gained mixed solution, rate of addition 3mL/min, continues
Continuous rotating speed 400rpm/min stirs 15min, obtains hydro-thermal presoma；
(5) hydro-thermal presoma is transferred in hydrothermal reaction kettle, is warming up to 190 DEG C with 12 DEG C/min heating rate, constant temperature
Naturally cool to room temperature after 6.0h and obtain hydrothermal product；
(6) hydrothermal product sequentially passes through deionized water and dehydrated alcohol respectively washs three times, 70 DEG C of dry 12.0h,
Ca4B10O19·7H2O microsphere.
The Ca that the present embodiment prepares4B10O19·7H2O microsphere is assembled by two-dimensional nano sheet, has multi-stage porous knot
Structure, particle diameter is in 6～12 μm, even particle size distribution.
Embodiment 8:
Hydration Calcium pyroborate (the Ca that embodiment 7 is obtained4B10O19·7H2O) during microsphere is placed in tube furnace, with 5 DEG C/min liter
Temperature ramp, to 750 DEG C, naturally cools to room temperature after roasting 6.0h, obtains Ca (BO2)2Microsphere.
Ca (the BO that the present embodiment prepares2)2Microsphere has hierarchical porous structure, and particle diameter is in 9～16 μm, and particle diameter distribution is all
Even.
As can be seen from the above embodiments, the present invention provide or the hydration Calcium pyroborate prepared according to preparation method of the present invention
Microsphere and anhydrous boric acid calcium microsphere have hierarchical porous structure, even particle size distribution.
The above is only the preferred embodiment of the present invention, and the present invention not makees any pro forma restriction.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to if making
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. it is hydrated a preparation method for Calcium pyroborate microsphere, comprises the following steps:
(1) calcium salt, alkali source and water are mixed, obtain mixed serum；
(2) mixed serum that described step (1) obtains is mixed with surfactant, obtain mixed solution；
(3) being mixed with boron source by the mixed solution that described step (2) obtains, hydro-thermal reaction obtains being hydrated Calcium pyroborate microsphere.
Preparation method the most according to claim 1, it is characterised in that Ca in described step (1) calcium salt2+With OH in alkali source-
Mol ratio be 1:2～4.
Preparation method the most according to claim 1, it is characterised in that the mole of surfactant in described step (2)
For Ca in described calcium salt2+The 1.6～50% of mole.
4. according to the preparation method described in claim 1 or 3, it is characterised in that described surfactant is citric acid, citric acid
One or more in sodium, disodiumedetate and ethylenediaminetetraacetic acid.
Preparation method the most according to claim 1, it is characterised in that the B in boron source and described calcium salt in described step (3)
Middle Ca2+Mol ratio be 1:2～4.
Preparation method the most according to claim 1, it is characterised in that in described step (3), the temperature of hydro-thermal reaction is 150
～210 DEG C, the pressure of hydro-thermal reaction is 0.12～0.23MPa, and the time of hydro-thermal reaction is 1～24h.
7. the hydration Calcium pyroborate microsphere that prepared by preparation method described in claim 1～6 any one, is assembled by nanometer sheet,
The particle diameter of described microsphere is 6～15 μm.
8. the preparation method of an anhydrous boric acid calcium microsphere, it is characterised in that enter being hydrated Calcium pyroborate microsphere described in claim 7
Row roasting, obtains anhydrous boric acid calcium microsphere.
Preparation method the most according to claim 8, it is characterised in that the temperature of described roasting is 650～750 DEG C, described
The time of roasting is 1～12h.
10. the anhydrous boric acid calcium microsphere that prepared by preparation method described in claim 8 or 9, the particle diameter of described microsphere is 9～16 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610369590.4A CN106082252B (en) | 2016-05-28 | 2016-05-28 | A kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610369590.4A CN106082252B (en) | 2016-05-28 | 2016-05-28 | A kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106082252A true CN106082252A (en) | 2016-11-09 |
| CN106082252B CN106082252B (en) | 2018-05-25 |
Family
ID=57230738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610369590.4A Expired - Fee Related CN106082252B (en) | 2016-05-28 | 2016-05-28 | A kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106082252B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809426A (en) * | 2019-03-01 | 2019-05-28 | 安徽壹石通材料科技股份有限公司 | The water-bath of ultra-fine flower-shaped line borate fire retardant-hydro-thermal linkage synthesis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1252775A (en) * | 1997-04-18 | 2000-05-10 | 美国博拉克有限公司 | Method for producing calcium borate |
| CN103011187A (en) * | 2012-12-14 | 2013-04-03 | 陕西师范大学 | Preparation method of nano-sized CaO.3 B2o3.4 H2O |
| CN104556082A (en) * | 2015-01-14 | 2015-04-29 | 景德镇陶瓷学院 | Preparation method for calcium borate |
| CN104817094A (en) * | 2015-04-24 | 2015-08-05 | 曲阜师范大学 | Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method |
-
2016
- 2016-05-28 CN CN201610369590.4A patent/CN106082252B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1252775A (en) * | 1997-04-18 | 2000-05-10 | 美国博拉克有限公司 | Method for producing calcium borate |
| CN103011187A (en) * | 2012-12-14 | 2013-04-03 | 陕西师范大学 | Preparation method of nano-sized CaO.3 B2o3.4 H2O |
| CN104556082A (en) * | 2015-01-14 | 2015-04-29 | 景德镇陶瓷学院 | Preparation method for calcium borate |
| CN104817094A (en) * | 2015-04-24 | 2015-08-05 | 曲阜师范大学 | Hydration and anhydrous multistage porous calcium borate microsphere low-temperature hydrothermal-thermal conversion synthetic method |
Non-Patent Citations (2)
| Title |
|---|
| ZHAOQIANG ZHANG ET AL.: ""Hierarchical porous Ca(BO2)2 microspheres: Hydrothermal–thermal conversion synthesis and their applications in heavy metal ions adsorption and solvent-free oxidation of benzyl alcohol"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| ZHI-HONG LIU ET AL.: ""Preparation of nanoplates assembled 4CaO•5B2O3•7H2O oval-like microspheres via a hydrothermal method"", 《MATERIALS LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809426A (en) * | 2019-03-01 | 2019-05-28 | 安徽壹石通材料科技股份有限公司 | The water-bath of ultra-fine flower-shaped line borate fire retardant-hydro-thermal linkage synthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106082252B (en) | 2018-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103708551B (en) | The preparation method of a kind of ethylene glycol-water mixed solvent thermal synthesis bismuth oxycarbonate flower-like microsphere | |
| CN104591301B (en) | A kind of porous nano CoFe 2o 4preparation method | |
| CN103466702B (en) | Method for preparing porous bismuth oxide nano-material without template | |
| CN102641736B (en) | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof | |
| Liu et al. | A simple and efficient synthetic route for preparation of NaYF 4 upconversion nanoparticles by thermo-decomposition of rare-earth oleates | |
| CN103071807A (en) | Preparation method of ultra-fine spherical cobalt powder | |
| CN104030335A (en) | Method for preparing Sm(OH)3/ZnO nano-composite by using homogeneous hydrothermal method | |
| CN101717108A (en) | Industrial preparation method of rare earth hydrate and oxide nano-rod | |
| CN103537237A (en) | Preparation method of Fe3O4@C@PAM core-shell magnetic nano material | |
| CN107500303B (en) | A kind of mesoporous magnesium silicate microballoon and its hydro-thermal-thermal transition preparation method | |
| CN103864032B (en) | A kind of preparation method of nano material | |
| CN104528799A (en) | Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder | |
| CN108083316A (en) | A kind of preparation method of nano rareearth oxidate powder body | |
| CN105032397A (en) | Method for synthesizing bismuth vanadate photocatalyst through starch self-combustion | |
| CN102951686A (en) | Preparation method for granular manganese tungstate nanocrystals | |
| CN106185965A (en) | The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide | |
| CN106315690A (en) | Porous cobalt tetroxide nanosheet and preparation method thereof | |
| CN100486895C (en) | Preparation method for nanometer magnesium oxide | |
| CN102659154A (en) | Method for preparing nano alpha-Al2O3 powder | |
| CN106082252A (en) | A kind of hydration Calcium pyroborate microsphere, anhydrous boric acid calcium microsphere and preparation method thereof | |
| CN105883910A (en) | Preparation method and product for perovskite SrTiO3 porous nano particles | |
| CN101786669B (en) | Alpha-ferric oxide mesoscopic crystal preparation method | |
| CN105329870B (en) | A kind of magic square shape sillenite Bismugel (Biothrax). raw powder's production technology | |
| CN102618279B (en) | Preparation method of shape-controllable aluminate luminous materials | |
| CN101559968B (en) | Preparation method of high-purity nano yttrium-based oxide powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20180525 |