CN106082252B - A kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon and preparation method thereof - Google Patents
A kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon and preparation method thereof Download PDFInfo
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- 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
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Abstract
The present invention provides a kind of hydration line borate microballoon and anhydrous boric acid calcium microballoon and preparation method thereof.The present invention uses hydro-thermal thermal conversion process, using calcium salt, boron source and alkali source as raw material, by adding in surfactant in aqueous solution, Effective Regulation product forms and pattern, the hydration line borate microballoon of size uniformity is obtained through hydro-thermal reaction, fired raising crystallinity again obtains the anhydrous boric acid calcium microballoon of size uniformity, is expected to be used widely containing heavy metal ion or the fields such as dye wastewater treatment, supported catalyst, fire-retardant.Preparation method provided by the invention is easy to operate, mild condition, low energy consumption, of low cost, technique is easily-controllable, is promoted suitable for large-scale industry.
Description
Technical field
The present invention relates to technical field of inorganic chemical industry, more particularly to a kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon
And preparation method thereof.
Background technology
In recent years, three-dimensional multistage structure nano material is due to haveing excellent performance, unique structure, and specific surface area is high, mechanical strength
The advantages that good and be concerned, and be widely used in energy storage, sensor, water process, the fields such as catalyst carrier.Due to boron
The changeable composition of hydrochlorate and its special performance in various fields and potential application receive more and more concerns.Wherein, boron
Sour calcium is widely used as fire retardant, and it is industrial to can be also used for white pigment, ceramics, glass, papermaking, rubber and plastics etc..Synthesis
The cost of line borate is equivalent to 1.3 times of boric acid price, is the minimum fire retardant of cost, and the boric acid with three-dimensional multistage structure
Calcium more becomes research hotspot.
At present, the line borate of three-dimensional multistage structure mainly synthesizes to obtain using hydro-thermal method, solvent-thermal method and solid reaction process.
Solvent-thermal method has the regulation and control of three-dimensional appearance certain help, but most of organic solvent pair using organic solvent as reaction medium
Human health, the waste water generated in last handling process easily cause water pollution；Solid reaction process is compared to obtained by other methods
Product thermal stability is high, but severe reaction conditions, and energy consumption is big, and product morphology is inhomogenous.Therefore, in comparison, hydro-thermal method
It is a kind of method for the synthesis three-dimensional multistage structure line borate being widely used.
Zhu, W.C. etc. report a kind of multistage hydration line borate (Ca assembled by losenges4B10O19·7H2O) surpass
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 the product size is larger, and since losenges and the Interaction Force of piece are weak, causes product pellet stability inclined
De-assembly easily occurs for difference, it is impossible to which fired processing obtains anhydrous boric acid calcium；The Chinese patent of Publication No. CN104817094A
Also disclose that a kind of method that hydration and the porous line borate microballoon of anhydrous multistage are prepared by hydro-thermal-thermal transition, but the said goods
Particle morphology homogeneity is poor, and microsphere surface relative smooth is fine and close, and pore structure is not abundant enough, and microballoon size is uneven, diameter distribution
It is wide in range.
The content of the invention
It is an object of the invention to provide a kind of hydration line borate microballoon, anhydrous boric acid calcium microballoon and preparation method thereof, purports
A kind of thermal stability is good, has hydration line borate microballoon, the anhydrous boric acid calcium microballoon of hierarchical porous structure and size uniform providing
And preparation method thereof.
The present invention provides a kind of preparation methods for being hydrated line borate microballoon, comprise the following steps：
(1) calcium salt, alkali source and water are mixed, obtains mixed serum；
(2) mixed serum that the step (1) obtains with surfactant is mixed, obtains mixed solution；
(3) mixed solution that the step (2) obtains is mixed with boron source, hydro-thermal reaction obtains hydration line borate microballoon.
Preferably, Ca in step (1) calcium salt2+Molar ratio with OH- in alkali source is 1:2~4.
Preferably, the mole of surfactant is Ca in the calcium salt in the step (2)2+The 1.6 of mole~
50%.
Preferably, the surfactant is citric acid, sodium citrate, disodium ethylene diamine tetraacetate and ethylenediamine tetra-acetic acid
In one or more.
Preferably, the B in the step (3) in boron source and Ca in the calcium salt2+Molar ratio be 1:2~4.
Preferably, in the step (3) temperature of hydro-thermal reaction for 150~210 DEG C, the pressure of hydro-thermal reaction for 0.12~
0.23MPa, time of hydro-thermal reaction for 1~for 24 hours.
The present invention also provides hydration line borate microballoon prepared by preparation method described in above-mentioned technical proposal, by nanometer sheet group
It fills, the grain size of the microballoon is 6~15 μm.
The present invention also provides a kind of preparation methods of anhydrous boric acid calcium microballoon, boric acid will be hydrated described in above-mentioned technical proposal
Calcium microballoon is roasted, and obtains anhydrous boric acid calcium microballoon.
Preferably, the temperature of the roasting is 650~750 DEG C, and the time of the roasting is 1~12h.
The present invention also provides anhydrous boric acid calcium microballoon prepared by above-mentioned technical proposal the method, the grain sizes of the microballoon
For 9~16 μm.
The present invention is using hydro-thermal-thermal conversion process, using calcium salt, boron source and alkali source as raw material, by adding in aqueous solution
Surfactant, Effective Regulation product composition and pattern, obtain the hydration line borate microballoon of size uniformity through hydro-thermal reaction, then pass through
Roasting improves crystallinity, obtains the anhydrous boric acid calcium microballoon of size uniformity, be expected to containing heavy metal ion or dye wastewater treatment,
It is used widely in the fields such as supported catalyst, fire-retardant.The experimental results showed that the hydration boron that method provided by the invention is prepared
Sour calcium microballoon and anhydrous boric acid calcium microballoon are with hierarchical porous structure, and thermal stability is good, uniform particle sizes, are hydrated line borate microballoon
Grain size for 6~15 μm, the grain size of the anhydrous boric acid calcium microballoon is 9~16 μm.
Preparation method provided by the invention is easy to operate, mild condition, low energy consumption, of low cost, technique is easily-controllable, suitable for big
Technical scale is promoted.
Description of the drawings
Fig. 1 is the XRD spectrum of the hydration line borate microballoon obtained in embodiment 1；
Fig. 2 is the SEM image of the hydration line borate microballoon obtained in embodiment 1；
Fig. 3 is the XRD spectrum of the anhydrous boric acid calcium microballoon obtained in embodiment 2；
Fig. 4 is the SEM image of the hydration line borate microballoon obtained in embodiment 3；
Fig. 5 is the SEM image of the anhydrous boric acid calcium microballoon obtained in embodiment 6.
Specific embodiment
The present invention provides a kind of preparation methods for being hydrated line borate microballoon, comprise the following steps：
(1) calcium salt, alkali source and water are mixed, obtains mixed serum；
(2) mixed serum that the step (1) obtains with surfactant is mixed, obtains mixed solution；
(3) mixed solution that the step (2) obtains is mixed with boron source, hydro-thermal reaction obtains hydration line borate microballoon.
The present invention mixes calcium salt, alkali source and water, obtains mixed serum.The present invention is not special to the operation of the mixing
Restriction, using the method well known to those skilled in the art for preparing mixed serum.The present invention is preferably first by calcium salt and water
It is mixed, obtains calcium salt soln；The calcium salt soln with alkali is mixed again, obtains mixed serum.In the present invention, it is described mixed
Conjunction preferably carries out under agitation.In the present invention, the stirring is preferably magnetic agitation；The rate of the stirring is preferably
350~450rpm/min；The time of the stirring is preferably 5~10min.In the present invention, Ca in the calcium salt soln2+Rub
Your concentration is preferably 0.5~2mol/L, more preferably 1~1.5mol/L.
For calcium salt is made fully to be reacted with alkali source, it is molten that the alkali source is preferably added drop-wise to the calcium salt by the present invention in the form of a solution
It carries out being mixed to get mixed serum in liquid.In the present invention, the molar concentration of the alkali source solution is preferably 1~8mol/L, more
Preferably 3~5mol/L.In the present invention, the rate of the dropwise addition is preferably 2.5~3.5mL/min.In the present invention, it is described
Mixing preferably carries out under agitation.In the present invention, the stirring is preferably magnetic agitation；The rate of the stirring is preferred
For 350~450rpm/min；The time of the stirring is preferably 10~15min.
In the present invention, the calcium salt is preferably soluble calcium salt, more preferably in calcium nitrate, calcium chloride and calcium acetate
It is one or more.In the present invention, isolate and purify for convenience, improve the purity of product, the calcium salt be most preferably calcium nitrate,
One kind in calcium chloride and calcium acetate.The present invention does not have the species of the alkali source special restriction, using people in the art
Alkali source known to member.In order to avoid the defects of dangerous big, environmental pollution is greatly existing for organic base and amplification is difficult, at this
In invention, the alkali source is preferably inorganic alkali source, more preferably inorganic soluble alkali source, can be specifically soluble hydroxide
Object is most preferably potassium hydroxide and/or sodium hydroxide；It isolates and purifies for convenience, improves the purity of product, the alkali source is optimal
Elect potassium hydroxide or sodium hydroxide as.In the present invention, the water is preferably deionized water.
In the present invention, Ca in the calcium salt2+With OH in the alkali source-Molar ratio be preferably 1:2~4, more preferably
1:2.5~3.5.
After obtaining mixed serum, the present invention mixes the mixed serum with surfactant, obtains mixed solution.At this
In invention, the mole of the surfactant is preferably Ca in the calcium salt2+The 1.6~50% of mole, more preferably 10
~30%, it is most preferably 20~25%.In the present invention, the surfactant is preferably citric acid, sodium citrate, ethylenediamine
One or more in tetraacethyl disodium and ethylenediamine tetra-acetic acid；It isolates and purifies for convenience, improves the purity of product, the table
Face activating agent is more preferably one kind in citric acid, sodium citrate, disodium ethylene diamine tetraacetate and ethylenediamine tetra-acetic acid.
The present invention preferably adds in the surfactant in mixed serum, stirs to get mixed solution.In the present invention,
The surfactant can be with Ca in solution2+Reaction forms chelate, reduces Free Ca in solution2+Concentration, so as to control production
Object slowly generates, and nanometer sheet oriented growth and self assembly is promoted to generate, and size is smaller and uniform, the uniform microballoon of pattern.In this hair
In bright, the stirring is preferably magnetic agitation；The rate of the stirring is preferably 350~450rpm/min；The stirring when
Between be preferably 10~20min, more preferably 14~16min.
After obtaining mixed solution, the present invention mixes the mixed solution with boron source, and hydro-thermal reaction obtains hydration line borate.
In the present invention, B and Ca in the calcium salt in the boron source2+Molar ratio be preferably 1:2~4, more preferably 1:2.5~3.5.
In the present invention, the boron source is preferably boric acid and/or borax, is isolated and purified for convenience, improves the purity of product, the boron
Source is more preferably boric acid or borax.
For reactant is made more fully to mix, promote particle form more uniform, the present invention is preferably by the boron
Source, which is added drop-wise in the form of a solution in the mixed solution, to carry out being mixed to get hydro-thermal presoma.In the present invention, the boron source is molten
Liquid is preferably the aqueous solution of boron source；The molar concentration of the boron source solution is preferably 0.2~0.8mol/L, more preferably 0.3~
0.6mol/L.In the present invention, the rate of the dropwise addition is preferably 2.5~3.5mL/min.In the present invention, the mixing is excellent
Choosing carries out under agitation.In the present invention, the stirring is preferably magnetic agitation；The rate of the stirring is preferably 350
~450rpm/min；The time of the stirring is preferably 10~20min, more preferably 14~16min.
After obtaining hydro-thermal presoma, the hydro-thermal presoma is carried out hydro-thermal reaction by the present invention, and it is micro- to obtain hydration line borate
Ball.The present invention does not have the device of the hydro-thermal reaction special restriction, using hydro-thermal reaction well known to those skilled in the art
Device.In the present invention, the hydro-thermal reaction carries out preferably in hydrothermal reaction kettle.In the present invention, the hydro-thermal
The temperature of reaction is preferably 150~210 DEG C, more preferably 170~190 DEG C, is 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 the hydro-thermal reaction
Heat preservation carries out hydro-thermal reaction, and time of the heat preservation is preferably 1~for 24 hours, more preferably 5~18h is most preferably 10~12h.
In the present invention, the rate for being warming up to the hydrothermal temperature is preferably 5~15 DEG C/min, more preferably 8~
12℃/min.In the present invention, the reaction temperature and time can regulate and control product into phase velocity from aerodynamic point, by ripe
Change mechanism promotes product pellet crystallinity and excessive temperature, undue growth caused by long-time excessively is avoided to obtain size uniform again simultaneously
Product.
In order to improve the purity of product, the present invention is preferably washed, filtered and dried to the product of the hydro-thermal reaction.
Operation no special restriction of the present invention to the washing and filtering, using washing well known to those skilled in the art, filtering
With dry operation.In the present invention, the detergent used that washs is preferably deionized water and ethyl alcohol.In the present invention
It is preferred that by obtained hydration line borate microballoon successively through respectively washing 3~5 times of deionized water and ethyl alcohol.In the present invention, the mistake
Filter is preferably to filter；The device of the suction filtration is preferably Buchner funnel.In the present invention, the temperature of the drying be preferably 70~
100 DEG C, more preferably 80~90 DEG C are most preferably 84~88 DEG C；The time of the drying is preferably 12~for 24 hours, more preferably
16~20h is most preferably 17~19h.
The present invention also provides hydration line borate microballoon prepared by preparation method described in above-mentioned technical proposal, by nanometer sheet group
It fills, the grain size of the microballoon is 6~15 μm more preferably 7~12 μm.In the present invention, the shape of the nanometer sheet is preferred
For hexagon, the thickness of the nanometer sheet is preferably 70~90nm, more preferably 75~85nm.
The present invention also provides a kind of preparation methods of anhydrous boric acid calcium microballoon, boric acid will be hydrated described in above-mentioned technical proposal
Calcium microballoon is roasted, and obtains anhydrous boric acid calcium microballoon.The present invention does not have the device of the roasting special restriction, using this
The device of roasting known to field technology personnel.In the present invention, the roasting carries out preferably in tube furnace.In this hair
In bright, the temperature of the roasting is preferably 650~750 DEG C, more preferably 680~720 DEG C, is most preferably 690~710 DEG C；
The time roasted under the calcination temperature is preferably 1~12h, more preferably 4~10h, is most preferably 6~8h.In the present invention,
The rate for being warming up to calcination temperature is preferably 1~10 DEG C/min, more preferably 4~6 DEG C/min.In the present invention, it is described
Roasting can realize Ca4B10O19·7H2O to Ca (BO2)2Phase transition, while improve anhydrous Ca (BO2)2The crystallinity of microballoon.
The present invention also provides anhydrous boric acid calcium microballoon prepared by above-mentioned technical proposal the method, the grain sizes of the microballoon
For 9~16 μm, more preferably 12~14 μm.
In order to further illustrate the present invention, with reference to embodiment to hydration line borate microballoon provided by the invention and anhydrous
The preparation method of line borate microballoon is described in detail, but cannot they be interpreted as limiting the scope of the present invention.
Embodiment 1:
(1) addition of 10mL deionized waters is filled in 5mmol calcium nitrate solid beakers, rotating speed 400rpm/min magnetic agitations
Mixed liquor is obtained after 10min；
(2) by 10mL 1molL-1KOH solution is added dropwise in mixed solution, rate of addition 3mL/min, continues rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) 0.3125mmol EDTA-2Na solids are added in mixed solution obtained by (2), rotating speed 400rpm/min is stirred
Mix 5min；
(4) 30mL is contained to the H of 20mmol3BO3Solution is added dropwise to mixed solution obtained by (3), rate of addition 3mL/min, after
Continuous rotating speed 400rpm/min stirring 15min, obtain 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 rates, constant temperature
1.0h rear cooled to room temperature obtains hydrothermal product；
(6) by deionized water and absolute ethyl alcohol, respectively washing three times, is filtered hydrothermal product with Buchner funnel successively, and 70 DEG C dry
Dry 12.0h, obtains Ca4B10O19·7H2O microballoons.
The Ca that the present embodiment is prepared4B10O19·7H2The XRD spectrum of O microballoons is as shown in Figure 1.It can be seen from the figure that
Ca4B10O19·7H2The XRD diagram of O microballoons matches preferably with XRD standard card JCPDS No.10-0463, illustrate product composition compared with
It is pure.
The Ca that the present embodiment is prepared4B10O19·7H2The SEM image of O microballoons is as shown in Figure 2.It can be seen from the figure that
Ca4B10O19·7H2O microballoons are assembled by the two-dimensional nano piece that size is 75nm, have hierarchical porous structure, grain size is in 7~12 μ
M, particle diameter distribution are uniform.
Embodiment 2:
Hydration line borate (the Ca that embodiment 1 is obtained4B10O19·7H2O) microballoon is placed in tube furnace, with 10 DEG C/min liters
Warm rate is warming up to 750 DEG C, roasts cooled to room temperature after 1.0h, obtains Ca (BO2)2Microballoon.
Ca (the BO that the present embodiment is prepared2)2Microballoon XRD spectrum is as shown in Figure 3.It can be seen from the figure that Ca (BO2)2
The XRD diagram of microballoon matches preferably with XRD standard card JCPDS No.78-1277, and with extraordinary crystallinity.
Ca (the BO that the present embodiment is prepared2)2Microballoon has hierarchical porous structure, and for grain size at 9~14 μm, particle diameter distribution is equal
It is even.
Embodiment 3:
(1) addition of 10mL deionized waters is filled in the beaker of 10mmol calcium chloride solids, rotating speed 400rpm/min magnetic force
Mixed liquor is obtained after stirring 10min；
(2) by 10mL 2molL-1NaOH solution be added dropwise in mixed solution, rate of addition 3mL/min, continue rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) 2.5mmol EDTA solids are added in mixed solution obtained by (2), rotating speed 400rpm/min stirrings 5min；
(4) 30mL is contained to the H of 20mmol3BO3Solution is added dropwise to mixed solution obtained by (3), rate of addition 3mL/min, after
Continuous rotating speed 400rpm/min stirring 15min, obtain hydro-thermal presoma；
(5) it will transfer in hydrothermal reaction kettle, 180 DEG C be warming up to 10 DEG C/min heating rates, it is natural after constant temperature 12.0h
It is cooled to room temperature to obtain hydrothermal product；
(6) by deionized water and absolute ethyl alcohol, respectively three times, 70 DEG C of dry 12.0h are obtained hydrothermal product for washing successively
Ca4B10O19·7H2O microballoons.
The Ca that the present embodiment is prepared4B10O19·7H2The SEM image of O microballoons is as shown in Figure 4.It can be seen from the figure that
Ca4B10O19·7H2O microballoons are assembled by two-dimensional nano piece, have hierarchical porous structure, for grain size at 8~14 μm, particle diameter distribution is equal
It is even.
Embodiment 4:
Hydration line borate (the Ca that embodiment 3 is obtained4B10O19·7H2O) microballoon is placed in tube furnace, with 1 DEG C/min liters
Warm rate is warming up to 650 DEG C, roasts cooled to room temperature after 12.0h, obtains Ca (BO2)2Microballoon.
Ca (the BO that the present embodiment is prepared2)2Microballoon has hierarchical porous structure, and for grain size at 10~15 μm, particle diameter distribution is equal
It is even.
Embodiment 5:
(1) addition of 10mL deionized waters is filled in the beaker of 20mmol calcium acetate solids, rotating speed 400rpm/min magnetic force
Mixed liquor is obtained after stirring 10min；
(2) KOH solution of 10mL 4mol L-1 is added dropwise in mixed solution, rate of addition 3mL/min, continues rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) 0.625mmol sodium citrate solids are added in mixed solution obtained by (2), rotating speed 400rpm/min stirrings
5min；
(4) the 30mL borax solns for containing 10mmol are added dropwise to mixed solution obtained by (3), rate of addition 3mL/min, after
Continuous rotating speed 400rpm/min stirring 15min, obtain 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 rates, constant temperature
Cooled to room temperature obtains hydrothermal product after 24.0h；
(6) by deionized water and absolute ethyl alcohol, respectively three times, 70 DEG C of dry 12.0h are obtained hydrothermal product for washing successively
Ca4B10O19·7H2O microballoons.
The Ca that the present embodiment is prepared4B10O19·7H2O microballoons are assembled by two-dimensional nano piece, have multi-stage porous knot
Structure, for grain size at 8~14 μm, particle diameter distribution is uniform.
Embodiment 6:
Hydration line borate (the Ca that embodiment 5 is obtained4B10O19·7H2O) microballoon is placed in tube furnace, with 2.5 DEG C/min
Heating rate is warming up to 700 DEG C, roasts cooled to room temperature after 3.0h, obtains Ca (BO2)2Microballoon.
Ca (the BO that the present embodiment is prepared2)2The SEM image of microballoon is as shown in Figure 5.It can be seen from the figure that Ca
(BO2)2Microballoon has hierarchical porous structure, and for grain size at 9~16 μm, particle diameter distribution is uniform.
Embodiment 7:
(1) addition of 10mL deionized waters is filled in the beaker of 10mmol calcium chloride solids, rotating speed 400rpm/min magnetic force
Mixed liquor is obtained after stirring 10min；
(2) by 10mL 2molL-1NaOH solution be added dropwise in mixed solution, rate of addition 3mL/min, continue rotating speed
400rpm/min stirs 10min, obtains mixed serum；
(3) 1.25mmol citric acid solids are added in mixed solution obtained by (2), rotating speed 400rpm/min stirrings
5min；
(4) the 30mL borax solns for containing 10mmol are added dropwise to mixed solution obtained by (3), rate of addition 3mL/min, after
Continuous rotating speed 400rpm/min stirring 15min, obtain 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 rates, constant temperature
Cooled to room temperature obtains hydrothermal product after 6.0h；
(6) by deionized water and absolute ethyl alcohol, respectively three times, 70 DEG C of dry 12.0h are obtained hydrothermal product for washing successively
Ca4B10O19·7H2O microballoons.
The Ca that the present embodiment is prepared4B10O19·7H2O microballoons are assembled by two-dimensional nano piece, have multi-stage porous knot
Structure, for grain size at 6~12 μm, particle diameter distribution is uniform.
Embodiment 8:
Hydration line borate (the Ca that embodiment 7 is obtained4B10O19·7H2O) microballoon is placed in tube furnace, with 5 DEG C/min liters
Warm rate is warming up to 750 DEG C, roasts cooled to room temperature after 6.0h, obtains Ca (BO2)2Microballoon.
Ca (the BO that the present embodiment is prepared2)2Microballoon has hierarchical porous structure, and for grain size at 9~16 μm, particle diameter distribution is equal
It is even.
As can be seen from the above embodiments, hydration line borate that is provided by the invention or being prepared according to preparation method of the present invention
Microballoon and anhydrous boric acid calcium microballoon have hierarchical porous structure, and particle diameter distribution is uniform.
The above is only the preferred embodiment of the present invention, not makees limitation in any form to the present invention.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of preparation method for being hydrated line borate microballoon, comprises the following steps：
(1) calcium salt, alkali source and water are mixed, obtains mixed serum；Ca in the calcium salt2+With OH in alkali source-Molar ratio be 1:2
~4；
(2) mixed serum that the step (1) obtains with surfactant is mixed, obtains mixed solution；The surface-active
Agent is the one or more in citric acid, sodium citrate, disodium ethylene diamine tetraacetate and ethylenediamine tetra-acetic acid；
(3) mixed solution that the step (2) obtains is mixed with boron source, hydro-thermal reaction obtains hydration line borate microballoon；It is described
The temperature of hydro-thermal reaction is 150~210 DEG C, and the pressure of hydro-thermal reaction is 0.12~0.23MPa, time of hydro-thermal reaction for 1~
24h。
2. preparation method according to claim 1, which is characterized in that the mole of surfactant in the step (2)
For Ca in the calcium salt2+The 1.6~50% of mole.
3. preparation method according to claim 1, which is characterized in that B and the calcium salt in the step (3) in boron source
Middle Ca2+Molar ratio be 1:2~4.
4. hydration line borate microballoon prepared by preparation method described in claims 1 to 3 any one, is assembled by nanometer sheet,
The grain size of the hydration line borate microballoon is 6~15 μm.
5. a kind of preparation method of anhydrous boric acid calcium microballoon, which is characterized in that will described in claim 4 be hydrated line borate microballoon into
Row roasting, obtains anhydrous boric acid calcium microballoon.
6. preparation method according to claim 5, which is characterized in that the temperature of the roasting is 650~750 DEG C, described
The time of roasting is 1~12h.
7. anhydrous boric acid calcium microballoon prepared by the preparation method of claim 5 or 6, the grain size of the anhydrous boric acid calcium microballoon are
9~16 μm.
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| CN104556082A (en) * | 2015-01-14 | 2015-04-29 | 景德镇陶瓷学院 | Preparation method for calcium borate |
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| 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 |
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| 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 |
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