CN108314054A - A method of preparing microporous calcium silicate powder - Google Patents
A method of preparing microporous calcium silicate powder Download PDFInfo
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- CN108314054A CN108314054A CN201810292147.0A CN201810292147A CN108314054A CN 108314054 A CN108314054 A CN 108314054A CN 201810292147 A CN201810292147 A CN 201810292147A CN 108314054 A CN108314054 A CN 108314054A
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- C01B33/00—Silicon; Compounds thereof
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Abstract
Use high-purity quartz powder and high-quality lime stone as raw material the invention discloses a kind of, the method for producing micropore hydration calcium silicate powder material using hydrothermal synthesis reaction.Compared with existing calcium silicates synthesis technology, this method is extensive with raw material sources, is easy to get at a low price, the microstructure and crystallization degree of C S H gelling objects is can control by adjusting reaction condition, to meet different requirements.The microporous calcium silicate product microstructure that this method obtains physically well develops, have the characteristics that specific surface area, whiteness, bulk density are high, there is reinforcing property and chemical bond activity simultaneously, can be used as functional form chemical filler and be widely used in the use of the industries such as papermaking, plastics, rubber.
Description
Technical field
The present invention relates to chemical engineering and field of material engineering technology more particularly to a kind of use silica flour and lime masonrys
For raw material, the method for preparing microporous calcium silicate powder body material using hydro-thermal synthesis process and post-processing approach.
Background technology
Microporous calcium silicate powder body material belongs to one kind of hydrated calcium silicate, chemical formula CaOSiO2·nH2O, object phase
Composition is mainly C-S-H (I) types gel, C-S-H (II) type gels and unformed substance etc., and the material non-toxic is tasteless, insoluble
In Yu Shui, alcohol and aqueous slkali, but it is highly soluble in strong acid.Due to the powder body material fine size, whiteness is high, and bulk density and true
Density is relatively low, and heat-insulating property is preferable, therefore this kind of microporous calcium silicate powder both can be applied to field of heat insulating materials, also can be used as
Chemical industry additive is widely used in rubber, plastics, papermaking, paint field.
Artificial synthesized calcium silicates is usually by silicon such as flyash desiliconization liquid, soluble glass of high modulus, sodium silicate solution, diatomite
The calcium sources such as source and quick lime, milk of lime and calcium hydroxide powder carry out hydrothermal synthesis.Wherein current industrialization it is more be using height
Aluminium/high silica flour coal ash, as silicon source, is come as the desiliconization liquid obtained after raw material low pressure alkali soluble desiliconization using milk of lime as calcium source
Calcium silicates is prepared, this method has the shortcomings that following aspects：
1, usual flyash carries out desilication reaction, the amorphous state in flyash using low-concentration alkali liquor under lower pressure
SiO2It is easier to be dissolved in lye under this condition, and crystalline silica is relatively insoluble in lye, therefore the dissolution rate of silica is relatively low,
Obtained desiliconization liquid concentration also corresponding relatively low, wherein SiO2Content is generally in 30~80g/L, NaO2Content is generally on the left sides 50g/L
The right side, modulus 0.5~1.0 or so, this result in flyash desiliconization prepare sodium silicate solution reaction process energy consumption it is higher.In addition
Under this process conditions, the washing after flyash desiliconization also generates a large amount of washings, also phase after calcium silicates synthesis and filtration washing
A large amount of sig waters should be generated to need to recycle enrichment recycling, also exacerbate the energy consumption and water consume that later stage lye recycles.
2, the flyash that power plant generates is influenced by many factors such as coal constituent, power plant's furnace type structure, operating conditions,
Cause larger even if the image of areal flyash composition and microstructural differences s, then difference is more for the flyash of different regions
Greatly.Therefore using the amorphous silica in flyash as the siliceous raw material of calcium silicates, there is more demanding to flyash ask
Topic, causes its raw material sources not extensive enough, and region limitation is larger.
3, calcium silicates prepared by traditional handicraft, the siloxy on surface and silanol group functional group are by water molecules, wherein also
There are part functional group and the Na in the sig water of non-washes clean+Ion is combined closely, cause calcium silicate powder surface-active it is poor,
Specific surface area and the relatively low problem of oil factor；In addition also without being handled by dusting in calcium silicates drying process, a large amount of particulates
It is agglomerated into bulky grain under the action of combining water, directly affects the architectural characteristic and performance of material, without maximumlly
Play the characteristic of calcium silicates.
Invention content
The purpose of the present invention is to provide one kind prepared using high-purity ground quartz, lye and lime stone as primary raw material it is micro-
The method of hole calcium silicate powder, to solve the poor calcium silicate powder surface-active that the prior art produces, specific surface area and oil suction
It is worth relatively low problem, can maximumlly plays the characteristic of calcium silicates；Also have raw material sources range wide simultaneously, is limited by region
The advantages of system is smaller and can reduce energy consumption and water consume.
To achieve the above object, the technical solution adopted in the present invention is：
A method of microporous calcium silicate powder is prepared, the described method comprises the following steps：
(1) preparation of sodium silicate solution：High-purity quartz powder is chosen, is distributed to be formed in sodium hydroxide solution and is homogenized
The sodium silicate solution of acquisition is carried out concentration allotment by liquid after coarse filtration and refined filtration in surge-tank, SiO in solution after allotment2It is dense
Degree is in 40~80g/L, NaO2Sodium silicate solution of the concentration after 50~80g/L, allotment is spare as siliceous raw material；
(2) preparation of milk of lime：High-grade lime stone is chosen, it is mixed with stone coal after being crushed, washing stone, sorting
High-temperature calcination is carried out after closing uniformly, the quick lime obtained after calcining is through being sieved and being digested using hot water, after filtering, adjustment
It is spare as calcareous raw material after a concentration of 85~135g/L of milk of lime CaO, ageing 8~15h, preferably 12h；
(3) hydrothermal synthesis of calcium silicates：By sodium silicate solution obtained above and milk of lime according to CaO and SiO2Mole
Than 1.0, water consolidates mass ratio 7.5~13.5:1 progress dispensing is simultaneously uniformly mixed, and mixed liquor is warming up to 85 in hydro-thermal reaction container
~100 DEG C, soaking time control is 0.75~1.5h, and in insulating process, mixing speed is controlled in 150~200rpm；
(4) post-processing of microporous calcium silicate powder：After the completion of hydrothermal synthesis reaction, obtained slurry is filtered, is washed
Wash and obtain wet cake after being surface-treated, to wet cake carry out drying and dusting after to get microporous calcium silicate powder.
In the preparation process of the sodium silicate solution, the high-purity quartz powder is obtained by following steps：Choose SiO2
The glass sand of content >=99%, total impurities are no more than 1%, wherein impurity F e2O3Content≤0.05%, MgO contain
Above-mentioned quartz sand is used milling equipment fine grinding as 20 microns of average grain diameter hereinafter, the stone of moisture content≤3% by amount≤0.04%
Ying Fen.
Further, further comprising the steps of in the preparation process of the sodium silicate solution：By the high-purity quartz powder
It is distributed to 4.0kmol/m3~10.0kmol/m3Sodium hydroxide solution in form homogeneous slurry, silica flour and sodium hydroxide solution
Middle Na2The mass ratio of O is 1:0.5~1:1；0.6~0.8MPa of reaction pressure；158.9~170.4 DEG C of reaction temperature；Reaction
1.5~2.5h of time.
Further, further comprising the steps of in the preparation process of the sodium silicate solution：By the slurries after the completion of reaction
It being separated by solid-liquid separation, solid slag returns to silica flour feed inlet and recycles, and the sodium silicate solution obtained after filtering is coarse filtration liquid,
Refined filtration is carried out using leaf filter, leaf filter discharging floating material content≤0.02g/L is required after refined filtration.
In the preparation process of the milk of lime, the quick lime is obtained by following steps：Selection calcium oxide content >=
52%, iron oxide content≤0.3%, content of magnesia≤0.5%, SiO2The high-grade lime stone of content≤1.0%, by its into
After row is crushed, washes stone, sorting, control stone grain size is 55-74mm, then is mixed for 41-50mm stone coals with size
After uniformly, high-temperature calcination is carried out in steel construction shaft kiln.
Further, further comprising the steps of in the preparation process of the milk of lime：The quick lime obtained after calcining is passed through
After cinder, coal ash and granule quick lime are removed in sieving, using 65-95 DEG C of hot water according to lime：Weight ratio=1 of water:5~
1:7 mixing are digested, and the thick slurries of gained milk of lime are by 80~120 mesh straight line shakers or circular vibrating screen and cyclone hydraulic separators priority
The concentration of milk of lime is adjusted after filtering.
In the hydrothermal synthesis step of the calcium silicates, dispensing and after mixing is carried out, mixed liquor is in hydro-thermal reaction container
85~100 DEG C are inside warming up to, the heating-up time controls within the scope of 0.5h~0.75h, after reaching predetermined temperature, soaking time control
For 0.75~1.5h, in temperature-rise period, mixing speed controls in 200rpm~400rpm, insulating process, mixing speed control
In 150~200rpm.
In the post-processing step of the microporous calcium silicate powder, the calcium silicates wet cake wherein NaO after filtration washing2Content is wanted
It asks less than 1.2%, NaO in the microporous calcium silicate powder after drying2Content requirement is less than 2.0%.
Further, it is described surface treatment include, based on after filtering and washing gained calcium silicates butt quality 5%~
15% is added modifying agent, and the modifying agent is 2.5%~7% ethanol solution or 5%~8% acetone soln, is then used
10%~15% dilute hydrochloric acid based on calcium silicates butt quality is eluted and is moistened leaching.By above-mentioned surface treatment, silicon is played
Sour calcium surface texture purification and the effect of surface siloxy and the activation of silanol group functional group.
Optionally, the slurries after surface treatment are filtered with the wet cake for being 40%~80% to moisture content, modifying agent filter
It can be recycled after liquid recycling.
Further, after the surface treatment, drying is carried out to wet cake and dusting is handled, drying unit is usable but unlimited
In drying equipments such as pan dryers.
The microporous calcium silicate powder that through the invention prepared by the above method is the porosity with higher whiteness and purity, height
Adsorptivity and structural inorganic material.Its higher specific surface area, larger aperture, porosity and porosity characteristics make it be in
Reveal high oil absorption water imbibition and stronger strengthening action.It is tested by many experiments, apparent data target is filled out with traditional chemical industry
Material grade commodity GCC, PCC compare, and the main quality Heterosis of microporous calcium silicate powder of the present invention exists：Large specific surface area, sedimentation
Volume is high, proportion is small, and wearing valve is low (1.2mg), and retention of whiteness is good, and loss on ignition is small.It is analyzed from apparent data target, specific surface
Long-pending, ageing-resistant whiteness, wearing valve, Zeta potential, settling volume, chemical composition composition etc. are superior to general chemical filler.
The crystallization degree of microporous calcium silicate powder of the present invention is relatively low, and object phase constituent mainly contains unbodied water
Change gel of calcium silicate and for the compositions such as C-S-H (I) types gel, C-S-H (II) type gel, [SiO in C-S-H gels4]4-Silica
Tetrahedron constitutes layer structure, and [SiO4]4-The single-stranded of formation has been separately formed each layer, is then by calcium between layers
Atom carries out the multilayered structure constituted after bridging.There are siloxies and silanol group functional group for material surface as a result, there is very strong benefit
Epistasis can and be chemically combined performance, while have stronger chemisorption performance.C-S-H gels are with C-S- in microporous calcium silicate
H (I) types or C-S-H (II) type individually or are mixed.The microstructure of microporous calcium silicate powder particle is more with discrete honeycomb
Poroid the morphology of the aggregate exists, and there is the feature that stratiform crimps on surface, and spells the phenomenon that taking there is mutual again between layer structure, just
It is since stratiform spelling is taken thus constructs porous honeycomb structure.Above structure feature also shows the scrambling of distribution,
Meet unbodied hydrated calcium silicate feature, and different with crystal structure, thus the crystallinity of microporous calcium silicate powder and
The degree of order is not high.Loose porous and low-density the characteristic of microporous calcium silicate filler causes its crystal structure rigidly relatively low, this
It also explains microporous calcium silicate other conventional chemical fillers that compare and possesses relatively low wearing valve.It is more due to microporous calcium silicate powder
The inhomogeneities and these gaps of permeability and gap distribution are widely present all so that the filler has good optical property
With low-density advantage.Meanwhile the particle gap that porous surface and aggregation are formed is also to constitute microporous calcium silicate powder specific surface
The main reason for product is larger.
Compared with existing industrialized calcium silicates synthesis technology, the present invention mainly has the following advantages：
1, the primary raw material of production microporous calcium silicate powder uses high-purity ground quartz, lye and lime stone, above-mentioned raw materials
It is easy to get extensively, preparation is simple for siliceous raw material sodium silicate solution and calcareous raw material milk of lime, smaller by territory restriction.
2, using silica flour as siliceous raw material, the dissolving of concentration lye progress silicon is reacted in use under high pressure,
Concentration of lye and modulus can be effectively controlled, while the concentration of lye generated in calcium silicates building-up process is higher, alkali cycle
Energy consumption and water consume compared with use flyash be raw material technique be greatly lowered.
3, in the last handling process of synthetic calcium silicate, surface treatment and dry pulverization process are added so that preparation
Calcium silicate powder material has the dispersibility of better surface-active and microparticle, thus it is made to compare the silicon of traditional handicraft preparation
Sour calcium has better performance.
In conclusion the process of the present invention solves the main problem of traditional calcium silicates synthesis technology, and raw material
Be easy to get extensively, technical process it is simple and practicable, equipment requirement is low, smaller to existing calcium silicates synthesis technology and equipment change, pair sets
Standby to require to be relatively low, operability is higher, thus the present invention is easy to industrialization promotion.
Description of the drawings
Fig. 1 is microstructure electron microscope (the 10000 times of amplification photographs for the microporous calcium silicate powder that the embodiment of the present invention 1 obtains
Piece).
Fig. 2 is microstructure electron microscope (the 50000 times of amplification photographs for the microporous calcium silicate powder that the embodiment of the present invention 2 obtains
Piece).
Fig. 3 is that the microporous calcium silicate powder that the embodiment of the present invention 3 obtains is added into (100 times of micro-structure diagram after paper
Enlarged photograph).
Fig. 4 is that the microporous calcium silicate powder that the embodiment of the present invention 3 obtains is added into (5000 times of micro-structure diagram after paper
Enlarged photograph).
Specific implementation mode
The present invention is further described with reference to specific embodiment, the advantages and features of the present invention will be with describing
And it is apparent.But examples are merely exemplary for these, and it is not intended to limit the scope of the present invention in any way.Art technology
Personnel should be understood that without departing from the spirit and scope of the invention can be to the details and form of technical solution of the present invention
It modifies or replaces, but these modifications and replacement are each fallen in protection scope of the present invention..
Embodiment 1
Take SiO2Content 99.2%, Fe2O3Content 0.015%, content of MgO 0.01%, the high purity quartz of moisture content 2.5%
Powder 20g is then added to a concentration of 5.2kmol/m using flour mill fine grinding to 15 μm of grain size3Sodium hydroxide solution 81.43g
In, slurries are formed after stirring, the mass ratio for controlling sodium oxide molybdena and silica flour butt under this condition is 0.5:1, slurry temperature
165 DEG C are risen to, 1.7Mpa reacts 1.5h, is separated by solid-liquid separation after reaction to slurries with this condition, and by sodium silicate rough
Liquid passes through leaf filter refined filtration, and solid slag returns to silica flour feed inlet and recycles, obtained sodium silicate solution, SiO2Concentration
For 58g/L, as the siliceous raw material of hydrothermal synthesis calcium silicates.
Again by lime stone that stone pit obtains after being crushed, washing stone, classification, control size is 72mm, is made in shaft kiln
It is calcined with 45mm anthracites, after cinder (ash) and granule lime and lime dust are removed in obtained lime sieving, is broken for
After 20mm, the warm water for being 68 DEG C with temperature is according to lime：Water=1:5.5 mixing are digested, and the thick slurries of gained milk of lime pass through
80 mesh circular vibrating screens and cyclone hydraulic separators obtain refined lime lotion after successively filtering, adjustment refined lime breast CaO is a concentration of
125g/L and after being aged 12h, the calcareous raw material as microporous calcium silicate.
Sodium silicate solution obtained above and lime slurry are uniformly mixed, the calcium silicon in sodium metasilicate and lime slurry is controlled
Molar ratio 1.0, is warming up to 95 DEG C, heating-up time 0.5h, soaking time 1.5h in hydro-thermal reaction container, and mixing speed is
250rpm, in insulating process, mixing speed 180rpm.
After the completion of reaction, washing is filtered to the slurry of preparation, the calcium silicates wet cake after filtration washing, wherein NaO2Contain
Amount 1.1% is added the ethanol solution of 2.5% concentration according to the 7% of gained calcium silicates butt quality, finally uses calcium silicates butt
The dilute hydrochloric acid of 15% concentration of quality 10% is eluted and is moistened leaching, plays the purification of calcium silicates surface texture and surface siloxy
The effect activated with silanol group functional group.Slurries after surface treatment are filtered with the wet cake for being 55% to moisture content, it is modified
Agent filtrate recycling after recycle, finally to wet cake drying and dusting after, NaO2Content 1.8% finally obtains qualified micropore
Calcium silicate powder 16.08g.
Referring to Fig. 1, for microstructure electron microscope (the 10000 times of amplification photographs for the microporous calcium silicate powder that embodiment 1 obtains
Piece).
Embodiment 2
Take SiO2Content 99.6%, Fe2O3Content 0.030%, content of MgO 0.035%, the high purity quartz of moisture content 2.8%
Sand 20g is then added to a concentration of 7.4kmol/m using flour mill fine grinding to 17 μm of grain size3Sodium hydroxide solution 65.37g
In, slurries are formed after stirring, the mass ratio for controlling sodium oxide molybdena and silica flour butt under this condition is 0.6:1, slurry temperature
158 DEG C are risen to, 0.65Mpa reacts 2h, is separated by solid-liquid separation after reaction to slurries with this condition, and by sodium silicate rough
Liquid passes through leaf filter refined filtration, and solid slag returns to silica flour feed inlet and recycles, obtained sodium silicate solution, SiO2Concentration
For 50g/L, as the siliceous raw material of hydrothermal synthesis calcium silicates.
Again by lime stone that stone pit obtains after being crushed, washing stone, classification, control size is 68mm, is made in shaft kiln
It is calcined with 45mm anthracites, after cinder (ash) and granule lime and lime dust are removed in obtained lime sieving, is broken for
After 15mm, the warm water for being 80 DEG C with temperature is according to lime：Water=1:5.5 mixing are digested, and the thick slurries of gained milk of lime pass through
100 mesh straight line shakers and cyclone hydraulic separators obtain refined lime lotion after successively filtering, adjustment refined lime breast CaO is a concentration of
115g/L is simultaneously aged 12h, the calcareous raw material as microporous calcium silicate.
Sodium silicate solution obtained above and lime slurry are uniformly mixed, the calcium silicon in sodium metasilicate and lime slurry is controlled
Molar ratio 1.0, is warming up to 95 DEG C, heating-up time 0.6h, soaking time 1.0h in hydro-thermal reaction container, and temperature-rise period stirs
It is 280rpm to mix speed, in insulating process, mixing speed 160rpm.
After the completion of reaction, washing is filtered to the slurry of preparation, the calcium silicates wet cake after filtration washing, wherein NaO2Contain
The acetone soln of 5.5% concentration is added according to the 9% of gained calcium silicates butt quality in amount 0.95%, finally dry using calcium silicates
The dilute hydrochloric acid of 16% concentration of matrix amount 12% is eluted and is moistened leaching, plays the purification of calcium silicates surface texture and surface silica
The effect of base and the activation of silanol group functional group, is filtered the slurries after surface treatment the wet cake for being 52% to moisture content, changes
Property agent filtrate recycling after recycle.Finally to wet cake drying and dusting after, NaO2Content 1.4% finally obtains qualified micro-
Hole calcium silicate powder 15.53g.
Referring to Fig. 2, for microstructure electron microscope (the 50000 times of amplification photographs for the microporous calcium silicate powder that embodiment 2 obtains
Piece).
Embodiment 3
Take SiO2Content 99.5%, Fe2O3Content 0.045%, content of MgO 0.038%, the high purity quartz of moisture content 2.4%
Sand 20g is then added to a concentration of 8.5kmol/m using flour mill fine grinding to 12 μm of grain size3Sodium hydroxide solution 67.43g
In, slurries are formed after stirring, the mass ratio for controlling sodium oxide molybdena and silica flour butt under this condition is 1:1, slurry temperature liter
To 170.4 DEG C, 0.8Mpa reacts 2.5h, is separated by solid-liquid separation after reaction to slurries with this condition, and by sodium silicate rough
Liquid passes through leaf filter refined filtration, and solid slag returns to silica flour feed inlet and recycles, its SiO of obtained sodium silicate solution2Concentration
For 80g/L, as the siliceous raw material of hydrothermal synthesis calcium silicates.
Again by lime stone that stone pit obtains after being crushed, washing stone, classification, control size is 74mm, is made in shaft kiln
It is calcined with 50mm anthracites, after cinder (ash) and granule lime and lime dust are removed in obtained lime sieving, is broken for
After 25mm, the warm water for being 95 DEG C with temperature is according to lime：Water=1:7 mixing are digested, and the thick slurries of gained milk of lime pass through 120
Mesh straight line shaker and cyclone hydraulic separators obtain refined lime lotion, a concentration of 135g/ of adjustment refined lime breast CaO after successively filtering
L is simultaneously aged 12h, the calcareous raw material as microporous calcium silicate.
Sodium silicate solution obtained above and lime slurry are uniformly mixed, the calcium silicon in sodium metasilicate and lime slurry is controlled
Molar ratio 1.0 is warming up to 100 DEG C, heating-up time 0.75h, soaking time 1.5h, temperature-rise period in hydro-thermal reaction container
Mixing speed is 400rpm, in insulating process, mixing speed 200rpm.
After the completion of reaction, washing is filtered to the slurry of preparation, the calcium silicates wet cake after filtration washing, wherein NaO2Contain
Amount 0.85% is added the ethanol solution of 7% concentration according to the 15% of gained calcium silicates butt quality, finally uses calcium silicates butt
The dilute hydrochloric acid of 20% concentration of quality 15% is eluted and is moistened leaching, plays the purification of calcium silicates surface texture and surface siloxy
The effect activated with silanol group functional group is filtered the slurries after surface treatment the wet cake for being 80% to moisture content, modified
It is recycled after the recycling of agent filtrate.Finally to wet cake drying and dusting after, NaO2Content 0.55% finally obtains qualified micropore
Calcium silicate powder 16.84g.
Referring to Fig. 3 and Fig. 4, the microporous calcium silicate powder that respectively embodiment 3 obtains is added into the microstructure after paper
Scheme (100 times of enlarged photographs and 5000 times of enlarged photographs).
Following table 1 is the microporous calcium silicate powder and conventional papermaking filler physical property contrast table that above-described embodiment obtains.
Listed each physical-property parameter is by the microporous calcium silicate powder that is obtained in 3 embodiments wherein under first row " microporous calcium silicate "
The average value of respective physical nature parameters.As a result as follows：
1 microporous calcium silicate powder of table and conventional chemical industry filler rationality matter contrast table
Pass through the comparison of above-mentioned experimental data, it can be seen that microporous calcium silicate powder of the invention has the advantage that：①
Calcium silicate powder average grain diameter and particle diameter distribution prepared by the present invention is respectively 15.6 μm and 1.24, is superior to current prior art
It is more uniform thus preferably in papermaking, modeling to be embodied in powder granularity smaller, size distribution for the artificial synthesized calcium silicates prepared
It is added as functional stuffing in the fields such as material；2. possessing higher oil factor and specific surface area, it was demonstrated that material has and organic chemistry
Key and functional group preferably combine effect, can effectively improve and be filled with paper ink absorption and water imbibition, filler also can be improved and exist
Adding proportion in plastics；3. higher settling volume shows the millipore water calcium silicate material of this method synthesis in water phase point
There is better suspension, to be conducive to evenly dispersed and filler of the filler in fibre stuff and fibre in granular media system and slurry
The physics detention of dimension；4. the micropore hydrated calcium silicate of this process synthesis has higher specific surface area and whiteness, be conducive to
Imparting is filled with rear paper more preferably covering effect；It, should 5. calcium silicate powder synthesized by the present invention has high Zeta potential characteristic
Characteristic is combined with higher settling volume feature, is more advantageous to dispersion of the filler in pulping system, therefore synthetic microporous water
Change calcium silicate powder in Aqueous dispersions system and slurry while keeping well suspended and dispersion performance, passes through current potential spy
Property reinforce with the binding ability of fiber, be conducive to keeping for filler.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention belong to the scope of protection of present invention.
Claims (10)
1. a kind of method preparing microporous calcium silicate powder, which is characterized in that the described method comprises the following steps：
(1) preparation of sodium silicate solution：High-purity quartz powder is chosen, is distributed in sodium hydroxide solution and forms homogeneous slurry, is passed through
After coarse filtration and refined filtration, the sodium silicate solution of acquisition is subjected to concentration allotment in surge-tank, SiO in solution after allotment2Concentration exists
40~80g/L, NaO2Sodium silicate solution of the concentration after 50~80g/L, allotment is spare as siliceous raw material；
(2) preparation of milk of lime：High-grade lime stone is chosen, after being crushed, washing stone, sorting, is mixed with stone coal
High-temperature calcination is carried out after even, the quick lime obtained after calcining is through being sieved and being digested using hot water, after filtering, adjusts lime
Newborn a concentration of 85~135g/L of CaO, it is spare as calcareous raw material after being aged 8~15h；
(3) hydrothermal synthesis of calcium silicates：By sodium silicate solution obtained above and milk of lime according to CaO and SiO2Molar ratio
1.0, water consolidates mass ratio 7.5~13.5:1 progress dispensing is simultaneously uniformly mixed, and mixed liquor is warming up to 85 in hydro-thermal reaction container~
100 DEG C, soaking time control is 0.75~1.5h, and in insulating process, mixing speed is controlled in 150~200rpm；
(4) post-processing of microporous calcium silicate powder：After the completion of hydrothermal synthesis reaction, obtained slurry is filtered, wash and
Wet cake is obtained after surface treatment, to wet cake carry out drying and dusting after to get microporous calcium silicate powder.
2. the method according to claim 1 for preparing microporous calcium silicate powder, which is characterized in that in step (1), the height
Purity quartz powder is obtained by following steps：Choose SiO2The glass sand of content >=99%, total impurities are no more than
1%, wherein impurity F e2O3Content≤0.05%, MgO content≤0.04%, by above-mentioned quartz sand use milling equipment fine grinding
As 20 microns of average grain diameter hereinafter, the silica flour of moisture content≤3%.
3. the method according to claim 2 for preparing microporous calcium silicate powder, which is characterized in that in step (1), also wrap
It includes：The high-purity quartz powder is distributed to 4.0kmol/m3~10.0kmol/m3Sodium hydroxide solution in formed and be homogenized
Liquid, silica flour and Na in sodium hydroxide solution2The mass ratio of O is 1:0.5~1:1；0.6~0.8MPa of reaction pressure；Reaction
158.9~170.4 DEG C of temperature；1.5~2.5h of reaction time.
4. the method according to claim 3 for preparing microporous calcium silicate powder, which is characterized in that in step (1), also wrap
It includes：Slurries after the completion of reaction are separated by solid-liquid separation, solid slag returns to silica flour feed inlet and recycles, and is obtained after filtering
Sodium silicate solution be coarse filtration liquid, carry out refined filtration using leaf filter, require after refined filtration leaf filter discharging floating material content≤
0.02g/L。
5. the method according to claim 1 for preparing microporous calcium silicate powder, which is characterized in that in step (2), the life
Lime is obtained by following steps：Selection calcium oxide content >=52%, iron oxide content≤0.3%, content of magnesia≤
0.5%, SiO2The high-grade lime stone of content≤1.0% after being crushed, washing stone, sorting, controls stone grain size
For 55-74mm, then with size be 41-50mm stone coals after mixing, high-temperature calcination is carried out in steel construction shaft kiln.
6. the method according to claim 5 for preparing microporous calcium silicate powder, which is characterized in that in step (2), also wrap
It includes：By the quick lime obtained after calcining after cinder, coal ash and granule quick lime are removed in sieving, 65-95 DEG C of hot water is used
According to lime：Weight ratio=1 of water:5~1:7 mixing are digested, and the thick slurries of gained milk of lime pass through 80~120 mesh straight line shakers
Or the concentration of milk of lime is adjusted after the successively filtering of circular vibrating screen and cyclone hydraulic separators.
7. the method according to claim 1 for preparing microporous calcium silicate powder, which is characterized in that in step (3), matched
Expect and after mixing, mixed liquor be warming up to 85~100 DEG C in hydro-thermal reaction container, the heating-up time control 0.5h~
Within the scope of 0.75h, after reaching predetermined temperature, soaking time control is 0.75~1.5h, and in temperature-rise period, mixing speed control exists
200rpm~400rpm, in insulating process, mixing speed is controlled in 150~200rpm.
8. the method according to claim 1 for preparing microporous calcium silicate powder, which is characterized in that in step (4), cross diafiltration
Calcium silicates wet cake wherein NaO after washing2Content requirement is less than 1.2%, NaO in the microporous calcium silicate powder after drying2Content requirement
Less than 2.0%.
9. the method according to claim 8 for preparing microporous calcium silicate powder, which is characterized in that in step (4), the table
Surface treatment includes that modifying agent, the modifying agent is added in 5%~15% based on gained calcium silicates butt quality after filtering and washing
For 2.5%~7% ethanol solution or 5%~8% acetone soln, then use based on calcium silicates butt quality 10%~
15% dilute hydrochloric acid is eluted and is moistened leaching.
10. the method for preparing microporous calcium silicate powder according to any one of claim 1-9, which is characterized in that table
The wet cake that it is 40%~80% to moisture content that slurries after surface treatment, which are filtered, recycles after the recycling of modifying agent filtrate.
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| CN108821300A (en) * | 2018-08-06 | 2018-11-16 | 东北大学 | One kind preparing CaSiO by discarded silicon slag3Method |
| CN111170324A (en) * | 2020-01-21 | 2020-05-19 | 张战军 | Method for preparing light high-whiteness calcium silicate micro powder by using rice hull ash |
| CN111704143A (en) * | 2020-03-06 | 2020-09-25 | 宣全 | Production process for preparing composite calcium silicate by using rice hull ash |
| CN113082957A (en) * | 2021-03-29 | 2021-07-09 | 内蒙古工业大学 | Industrial flue gas sulfur dioxide removing agent and preparation method thereof |
| CN113149753A (en) * | 2021-03-23 | 2021-07-23 | 内蒙古工业大学 | Low-heavy-metal biogas residue composite organic silicon fertilizer with slow release function and preparation method thereof |
| CN114804689A (en) * | 2022-04-27 | 2022-07-29 | 廊谷(天津)新能源科技有限公司 | Preparation method of nano porous master batch for cement-based insulation board |
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| CN113149753A (en) * | 2021-03-23 | 2021-07-23 | 内蒙古工业大学 | Low-heavy-metal biogas residue composite organic silicon fertilizer with slow release function and preparation method thereof |
| CN113082957A (en) * | 2021-03-29 | 2021-07-09 | 内蒙古工业大学 | Industrial flue gas sulfur dioxide removing agent and preparation method thereof |
| CN114804689A (en) * | 2022-04-27 | 2022-07-29 | 廊谷(天津)新能源科技有限公司 | Preparation method of nano porous master batch for cement-based insulation board |
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