CN105670059B - Calcium silicate slag and calcium silicate slag base gum filler and preparation method thereof - Google Patents
Calcium silicate slag and calcium silicate slag base gum filler and preparation method thereof Download PDFInfo
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- CN105670059B CN105670059B CN201410659510.XA CN201410659510A CN105670059B CN 105670059 B CN105670059 B CN 105670059B CN 201410659510 A CN201410659510 A CN 201410659510A CN 105670059 B CN105670059 B CN 105670059B
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- 239000002893 slag Substances 0.000 title claims abstract description 158
- 239000000378 calcium silicate Substances 0.000 title claims abstract description 151
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 151
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000000945 filler Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011575 calcium Substances 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 24
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 24
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 24
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 76
- 239000002585 base Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 43
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000010909 process residue Substances 0.000 claims description 18
- 239000010881 fly ash Substances 0.000 claims description 16
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 235000010755 mineral Nutrition 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- -1 wherein Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 26
- 239000005060 rubber Substances 0.000 abstract description 26
- 230000003014 reinforcing effect Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 229910018626 Al(OH) Inorganic materials 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001576 calcium mineral Inorganic materials 0.000 description 1
- ZQNPDAVSHFGLIQ-UHFFFAOYSA-N calcium;hydrate Chemical compound O.[Ca] ZQNPDAVSHFGLIQ-UHFFFAOYSA-N 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of calcium silicate slag, the main component of the calcium silicate slag is Si and Ca, and also containing a small amount of Al, on the basis of the gross weight of calcium silicate slag, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35 40 weight %, CaO content be 35 40 weight %, Al2O3Content be 16 weight %, Ca/Si+Al molar ratio be 0.7 0.9.Also disclose the preparation method of calcium silicate slag and its calcium silicate slag of preparation, and calcium silicate slag base gum filler and preparation method thereof and its calcium silicate slag base gum filler prepared.The calcium silicate slag base gum filler of the present invention, has the reinforcing effect suitable with white carbon, can make the rubber of preparation have higher disruptive force, fracture tensile strength, tearing elongation etc.；And preparation process is simple, derive from a wealth of sources, it is cheap, the cost of manufacture of rubber can be significantly reduced.
Description
Technical field
The present invention relates to a kind of calcium silicate slag prepared from industrial residu, and in particular, to from aluminum-containing mineral or the alkali of waste residue
Calcium silicate slag prepared by method residue of aluminum-extracted, and the calcium silicate slag base gum filler produced based on this, and calcium silicate slag and silico-calcium
The preparation method of slag base gum filler.
Background technology
, it is necessary to add a variety of fillers to strengthen the performance of rubber during rubber system is standby.The most important filler of one of which
It is white carbon, it can strengthen the reinforcing property of rubber, that is, the disruptive force, fracture tensile strength, tearing for improving rubber are stretched
Long rate etc., makes rubber have practical value.But white carbon is on the high side, the manufacturing cost of rubber is added.Therefore, need
The cheap gum filler of white carbon can be substituted by finding.
Flyash is the inevitable outcome of coal-fired power plant, is the single industrial solid castoff of Largest In China.Coal ash lifting
Aluminium mainly has two major class of acid system and alkaline process, decomposes flyash by activation under the specified conditions such as acid or alkali, sial is separated.
Residue of aluminum-extracted after aluminum-extracted pulverized fuel ash is cheap, derives from a wealth of sources, if it is possible to and rationally it is used, turns waste into wealth, can be very big
Improve the added value of aluminum-extracted pulverized fuel ash.
The content of the invention
The object of the present invention is to provide a kind of new gum filler with reinforcing property, with the hard charcoal that alternative cost is high
It is black.The present invention is prepared with aluminum-containing mineral or the alkaline process residue of aluminum-extracted of waste residue, such as flyash alkaline process residue of aluminum-extracted as raw material
Calcium silicate slag, and calcium silicate slag base gum filler prepared with this.
On the one hand, the present invention provides a kind of calcium silicate slag, the main component of the calcium silicate slag is Si and Ca, is also contained on a small quantity
Al, on the basis of the gross weight of calcium silicate slag, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-40
The content of weight %, CaO are 35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-
0.9。
Second aspect, the present invention provides a kind of calcium silicate slag base gum filler, the main component of the filler is that particle diameter is
The calcium silicate slag of 600-1500 mesh, the main component of the calcium silicate slag is Si and Ca, also containing a small amount of Al, with the gross weight of calcium silicate slag
On the basis of amount, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-40 weight %, CaO content
For 35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-0.9.
The third aspect, the present invention provides a kind of preparation method of calcium silicate slag, the described method includes：By aluminum-containing mineral or useless
The alkaline process residue of aluminum-extracted of slag carries out dealkalize processing in lye, wherein, aluminum-containing mineral or waste residue are preferably flyash, the lye
It is preferably that sodium hydroxide is molten for the solution of at least one of sodium carbonate, industrial caustic soda, industry weight alkali, calcium hydroxide and lime
Liquid.
Fourth aspect, the present invention provides calcium silicate slag prepared by method as described above.
5th aspect, the present invention provides a kind of preparation method of calcium silicate slag base gum filler, the described method includes：By silicon
Calcium ground-slag is broken to 600-1500 mesh, wherein, the main component of the calcium silicate slag is Si and Ca, also containing a small amount of aluminium, with silico-calcium
On the basis of the gross weight of slag, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-40 weight %,
The content of CaO is 35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-0.9；It is preferred that
Ground, the main thing of the calcium silicate slag is mutually tobermorite.
6th aspect, the present invention provides calcium silicate slag base gum filler prepared by method as described above.
The calcium silicate slag base gum filler of the present invention, has the reinforcing effect suitable with white carbon, can make the rubber of preparation
Product has higher disruptive force, fracture tensile strength, tearing elongation etc., rubber is had practical value；And this hair
Bright calcium silicate slag base gum filler, preparation process is simple, derives from a wealth of sources, cheap, can significantly reduce the system of rubber
Make cost.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction pattern of calcium silicate slag prepared by the embodiment of the present invention 1.
Fig. 2 is the graph of pore diameter distribution of calcium silicate slag prepared by the embodiment of the present invention 1.
Fig. 3 is the particle size distribution figure of calcium silicate slag prepared by the embodiment of the present invention 1.
Fig. 4 is the size distribution curve of 1000 mesh and 3500 mesh calcium silicate slags.
Fig. 5 is the SEM spectrum of different grain size calcium silicate slag, wherein, (a) is the SEM spectrum of the calcium silicate slag without super crushing；
(b) be crushed to 1000 mesh calcium silicate slag SEM spectrum；(c) be crushed to 3500 mesh calcium silicate slag SEM spectrum.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the present invention provides a kind of calcium silicate slag, the main component of the calcium silicate slag is Si and Ca, is also contained on a small quantity
Al, on the basis of the gross weight of calcium silicate slag, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-40
The content of weight %, CaO are 35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-
0.9。
The main thing phase composition of the calcium silicate slag of the present invention is preferably tobermorite.Tobermorite is a kind of stratiform silicate hydrate
Calcium mineral, orthorhombic system, a kind of its molecular formula are Ca5Si6O16(OH)2·4H2O.Part Si in structure4+Can be by Al3+Substitute, replace
Generation amount reaches as high as more than 10 weight %.
In the preferred embodiment of the present invention, the main thing phase composition of calcium silicate slag is tobermorite, i.e. calcium silicate slag
In Si and Ca exist in the form of tobermorite, the molecular formula of tobermorite is Ca5Si6O16(OH)2·4H2O, which part
Si4+By Al3+Substitute, that is, form aluminium tobermorite, its molecular formula is Ca5Si5Al(OH)O17·5H2O, in addition with a small amount of
Calcite, its molecular formula are CaCO3。
Second aspect, the present invention provides a kind of calcium silicate slag base gum filler, it is 600-1500 mesh which, which contains particle diameter,
Calcium silicate slag.The main component of the calcium silicate slag is Si and Ca, also containing a small amount of Al, on the basis of the gross weight of calcium silicate slag, Si,
Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-40 weight %, CaO content be 35-40 weight
Measure %, Al2O3Content be 1-6 weight %.And the molar ratio of Ca/Si+Al is 0.7-0.9.
Preferably, the main thing phase composition of above-mentioned calcium silicate slag is tobermorite, i.e. Si in calcium silicate slag and Ca is to avenge silico-calcium
The form of stone exists, and the molecular formula of tobermorite is Ca5Si6O16(OH)2·4H2O, which part Si4+By Al3+Substitute, i.e. shape
Into aluminium tobermorite, its molecular formula is Ca5Si5Al(OH)O17·5H2O, in addition with a small amount of calcite, its molecular formula is
CaCO3。
It was found by the inventors of the present invention that the particle diameter of above-mentioned calcium silicate slag is 600-1500 mesh, during as gum filler, can play
The suitable reinforcing effect with white carbon, produces the rubber with practical value.Preferably, when the particle diameter of calcium silicate slag reaches
During 800-1200 mesh, its specific surface area reaches 300-400m2/ g, reinforcing effect further improve.
The third aspect, the present invention provides a kind of preparation method of calcium silicate slag, this method includes：By aluminum-containing mineral or waste residue
Alkaline process residue of aluminum-extracted dealkalize processing is carried out in lye, wherein, aluminum-containing mineral or waste residue are preferably flyash, and lye is carbonic acid
The solution of at least one of sodium, industrial caustic soda, industry weight alkali, calcium hydroxide and lime, is preferably sodium hydroxide solution.
It will be understood by those skilled in the art that dealkalize processing carries out generally in closed container.
The alkaline process residue of aluminum-extracted contains substantial amounts of silicon and calcium, also containing substantial amounts of alkali, can be used as byproduct from putting forward aluminium work
Factory obtains, and such cost further reduces.The technique for carrying aluminium for the alkaline process of aluminum-containing mineral or waste residue does not have any restrictions, can be with
Aluminium technique is carried using alkaline process commonly used in the art.The residue that various alkaline process commonly used in the art carry aluminium can be used in the present invention.
In the art, for the dealkalize of alkaline process residue of aluminum-extracted, generally carry out in water.But dealkalize in water, dealkalize speed
Degree is slow, and with the rise of temperature, dealkalize speed can be accelerated, but the phenomenon of residue expansion occurs.The present inventor is grinding
Study carefully middle discovery, the alkaline process residue of aluminum-extracted of aluminum-containing mineral or waste residue is subjected to dealkalize processing in lye, dealkalize speed is fast, dealkalize rate
Height, and be not in residue expansion issues.
Lye commonly used in the art may be incorporated for the dealkalize processing of the present invention, such as sodium carbonate, industrial caustic soda (hydroxide
Sodium), industry weight alkali (sodium acid carbonate), the solution of at least one of calcium hydroxide and lime, be preferably sodium hydroxide solution.
In the method for the present invention, the condition of dealkalize processing preferably includes：Concentration of lye is 20-100g/L, more preferably 60-
100g/L；Temperature is 100-200 DEG C, more preferably 130-180 DEG C；Time is 0.5-2h, more preferably 1-1.5h；Liquid stereoplasm amount
Than for 3-6, more preferably 4-5；Pressure is 0.1-1.5MPa, more preferably 0.27-1.0MPa.Under above-mentioned preferable case, energy
Dealkalize rate is enough further improved, the calcium silicate slag for making to be prepared has more preferable strengthening action.
Fourth aspect, the present invention provides calcium silicate slag prepared by method as described above.
The calcium silicate slag being prepared by method as described above can meet that main component is Si and Ca, also containing a small amount of
Al, on the basis of the gross weight of calcium silicate slag, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-
The content of 40 weight %, CaO is 35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-
0.9。
5th aspect, the present invention provides a kind of preparation method of calcium silicate slag base gum filler, this method includes：By silico-calcium
Ground-slag is broken to 600-1500 mesh, wherein, the main component of calcium silicate slag is Si and Ca, also containing a small amount of Al, with the total of calcium silicate slag
On the basis of weight, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be that 35-40 weight %, CaO containing
Measure as 35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-0.9.
In the preferred embodiment of the present invention, the Si in calcium silicate slag and Ca exists in the form of tobermorite, snow
The molecular formula of silicoglaserite is Ca5Si6O16(OH)2·4H2O, which part Si4+By Al3+Substitute, that is, form aluminium tobermorite,
Its molecular formula is Ca5Si5Al(OH)O17·5H2O, in addition with a small amount of calcite, its molecular formula is CaCO3。
The method according to the invention, as long as calcium silicate slag as described above is crushed to 600-1500 mesh, adds as reinforcing agent
It is added in rubber formulation, you can play the reinforcing effect suitable with white carbon, produce the rubber with practical value.But it is preferred that
In the case of, when calcium silicate slag is crushed to 800-1200 mesh, the calcium silicate slag base gum filler that is prepared can be further improved
Reinforcing effect.
6th aspect, the present invention provides calcium silicate slag base gum filler prepared by method as described above.
In the present invention, residue of aluminum-extracted dealkalize processing after another technical effect is that, its whiteness improve.Flyash alkaline process carries aluminium
Residue is a kind of brick-red powder, if thought of as gum filler, particularly colorful rubber filler is, it is necessary to improve its whiteness.
In the present invention, it is preferable that by alkaline process residue of aluminum-extracted alkali collection recycle so that further reduce technique into
This.
It will be understood by those skilled in the art that it is contemplated that substituted with the calcium silicate slag base gum filler of the present invention white
Carbon black has suitable strengthening action and cost-effective purpose to reach as gum filler with white carbon.Therefore, for system
Other raw materials and method of standby rubber can use various raw materials and method commonly used in the art without particular/special requirement.
Embodiment
The present invention is further illustrated for following embodiment, but is not intended to limit the present invention.
In the following Examples and Comparative Examples：
Flyash alkaline process residue of aluminum-extracted component is as follows：Unit：Weight %
| SiO2 | Al2O3 | TFe2O3 | CaO | Na2O | TiO2 |
| 27.53 | 1.88 | 2.21 | 28.57 | 27.05 | 2.01 |
Super crushing：Crushed using superfine powder comminution.
The chemical composition analysis method of calcium silicate slag：Full chemistry analysis method.
Embodiment 1
The present embodiment is used to illustrate calcium silicate slag base gum filler of the present invention and preparation method thereof.
In closed container, flyash alkaline process residue of aluminum-extracted is subjected to dealkalize processing in the sodium hydroxide solution of 80g/L,
Treatment temperature is 160 DEG C, time 1h, and the liquid of sodium hydroxide solution and flyash alkaline process residue of aluminum-extracted consolidates mass ratio as 5.Reaction
Pressure is saturated vapor pressure at this temperature.Calcium silicate slag is obtained after dealkalize, the chemical composition analysis of calcium silicate slag the results are shown in Table 1.
The X-ray powder diffraction pattern of calcium silicate slag is shown in Fig. 1, and graph of pore diameter distribution is shown in Fig. 2, and particle size distribution figure is shown in Fig. 3, SEM figures
Spectrum is shown in Fig. 5 (a).
Then 1000 mesh are crushed to by obtained calcium silicate slag is super, obtain the granularity point of calcium silicate slag base gum filler A1, A1
Cloth curve is shown in Fig. 4, and SEM spectrum is shown in Fig. 5 (b).
It will be seen from figure 1 that the main thing phase composition of the calcium silicate slag obtained after flyash alkaline process residue of aluminum-extracted dealkalize is snow
Silicoglaserite, wherein there is part Si4+By Al3+Substitute.
Figure it is seen that calcium silicate slag size distribution scope is 3-84nm, average pore size 28.465nm, with reference to
Fig. 5, it can be determined that the hole in calcium silicate slag is the Secondary Channel that tobermorite thin slice fibrous crystal intersects to form.
From figure 3, it can be seen that the particle size distribution scope of calcium silicate slag is 0.594-310 μm, D [4,3] is 55.4 μm,
Dv10 is 7.27 μm, and Dv50 is 41.2 μm, and Dv90 is 121 μm.
Can be seen that calcium silicate slag from Fig. 3, Fig. 4 and Fig. 5 is the aggregate with burr, and aggregate is by 0.1-5 μm wide of thin slice
Fibrous crystal interts intertexture and forms, and there are more gap between crystal.Calcium silicate slag sheet-like fiber knot through extra-fine grinding process
Structure is destroyed, and particle diameter has obvious reduction, and therefore, specific surface area will significantly increase.And from figure 5 it can be seen that it is crushed to
Substantially without bulk flaky crystal in the calcium silicate slag of 1000 mesh and 3500 mesh, but it is crushed into small crystallization.
Embodiment 2
The present embodiment is used to illustrate calcium silicate slag base gum filler of the present invention and preparation method thereof.
In closed container, flyash alkaline process residue of aluminum-extracted is subjected to dealkalize processing in the sodium hydroxide solution of 60g/L,
Treatment temperature is 130 DEG C, time 1.2h, and the liquid-solid ratio of sodium hydroxide solution and flyash alkaline process residue of aluminum-extracted is 4.Reaction pressure
Power is saturated vapor pressure at this temperature.Calcium silicate slag is obtained after dealkalize, the chemical composition analysis of calcium silicate slag the results are shown in Table 1.
The X-ray powder diffraction pattern of calcium silicate slag is similar with Fig. 1, and graph of pore diameter distribution is similar with Fig. 2, particle size distribution figure and figure
3 is similar, and SEM spectrum is similar with (a) in Fig. 5.
Then 800 mesh are crushed to by obtained calcium silicate slag is super, obtain calcium silicate slag base gum filler A2.
Embodiment 3
The present embodiment is used to illustrate calcium silicate slag base gum filler of the present invention and preparation method thereof.
In closed container, flyash alkaline process residue of aluminum-extracted is carried out at dealkalize in the sodium hydroxide solution of 100g/L
Reason, treatment temperature are 180 DEG C, time 1.5h, and the liquid-solid ratio of sodium hydroxide solution and flyash alkaline process residue of aluminum-extracted is 3.Instead
Pressure is answered as saturated vapor pressure at this temperature.Calcium silicate slag is obtained after dealkalize, the chemical composition analysis of calcium silicate slag the results are shown in Table 1.
The X-ray powder diffraction pattern of calcium silicate slag is similar with Fig. 1, and graph of pore diameter distribution is similar with Fig. 2, particle size distribution figure and figure
3 is similar, and SEM spectrum is similar with (a) in Fig. 5.
Then 1200 mesh are crushed to by obtained calcium silicate slag is super, obtain calcium silicate slag base gum filler A3.
Embodiment 4
The present embodiment is used to illustrate calcium silicate slag base gum filler of the present invention and preparation method thereof.
Method according to embodiment 1 prepares calcium silicate slag base gum filler, unlike, by the super crushing of obtained calcium silicate slag
To 600 mesh, calcium silicate slag base gum filler A4 is obtained.
Embodiment 5
The present embodiment is used to illustrate calcium silicate slag base gum filler of the present invention and preparation method thereof.
Method according to embodiment 1 prepares calcium silicate slag base gum filler, unlike, by the super crushing of obtained calcium silicate slag
To 1500 mesh, calcium silicate slag base gum filler A5 is obtained.
Embodiment 6
The present embodiment is used to illustrate calcium silicate slag base gum filler of the present invention and preparation method thereof.
Method according to embodiment 1 prepares calcium silicate slag base gum filler, unlike, the concentration of sodium hydroxide solution is
20g/L。
The chemical composition analysis of calcium silicate slag the results are shown in Table 1.
Then 1000 mesh are crushed to by obtained calcium silicate slag is super, obtain calcium silicate slag base gum filler A6.
Embodiment 7
The present embodiment is used to illustrate calcium silicate slag base gum filler of the present invention and preparation method thereof.
Method according to embodiment 1 prepares calcium silicate slag base gum filler, unlike, the temperature of dealkalize processing is 100 DEG C,
Time is 0.5h, and the liquid-solid ratio of sodium hydroxide solution and flyash alkaline process residue of aluminum-extracted is 4.Reaction pressure is full at this temperature
And vapour pressure.Calcium silicate slag is obtained after dealkalize.
The chemical composition analysis of calcium silicate slag the results are shown in Table 1.
Then 1000 mesh are crushed to by obtained calcium silicate slag is super, obtain calcium silicate slag base gum filler A7.
Comparative example 1
Method according to embodiment 1 prepares calcium silicate slag base gum filler, unlike, it will be obtained after dealkalize without super
The calcium silicate slag of crushing is as calcium silicate slag base gum filler D1.
Comparative example 2
Method according to embodiment 1 prepares calcium silicate slag base gum filler, unlike, by the super crushing of obtained calcium silicate slag
To 3500 mesh, calcium silicate slag base gum filler D2 is obtained.The size distribution curve of D2 is shown in Fig. 4, and SEM spectrum is shown in Fig. 5 (c).
Chemical composition analysis result (the unit of 1 calcium silicate slag of table：Weight %)
| SiO2 | Al2O3 | TFe2O3 | CaO | Na2O | |
| Embodiment 1 | 37.04 | 4.8 | 2.87 | 37.33 | 0.32 |
| Embodiment 2 | 37.17 | 4.92 | 2.71 | 37.21 | 1.82 |
| Embodiment 3 | 37.17 | 4.71 | 2.77 | 36.97 | 1.5 |
| Embodiment 4 | 37.04 | 4.8 | 2.87 | 37.33 | 0.32 |
| Embodiment 5 | 37.04 | 4.8 | 2.87 | 37.33 | 0.32 |
| Embodiment 6 | 35.47 | 4.33 | 2.48 | 35.61 | 4.64 |
| Embodiment 7 | 34.49 | 4.25 | 2.39 | 34.53 | 7.5 |
| Comparative example 1 | 37.04 | 4.8 | 2.87 | 37.33 | 0.32 |
| Comparative example 2 | 37.04 | 4.8 | 2.87 | 37.33 | 0.32 |
Preparation example
100g butadiene-styrene rubber is subjected to the 5min that plasticates in the range of 25-30 DEG C of roller temperature and under the conditions of roll spacing 0.1mm first, then
50g A1-A7, D1-D2 are mixed with 100g broken-down rubbers, 1g altaxes, 1g stearic acid, 3g zinc oxide and 1.75g sulphur respectively
After uniformly, 10min is kneaded under the conditions of 50-55 DEG C of roller temperature scope and roll spacing 0.5mm, film is put into mould again after calendering formation
In be pressed in vulcanizing press and vulcanize 25min under 145 DEG C and 10MPa pressure, obtain rubber R1-R7 and R1 '-R2 ',
And set rubber B1 and B2 not filled and that filler is done with white carbon.
Test case
Disruptive force, fracture tensile strength, tearing elongation：Carried out according to GB/T 528-1998.
The disruptive force, fracture tensile strength and tearing elongation of above-mentioned each rubber are measured respectively, the results are shown in Table 2.
Table 2
According to table 2, R1-R7 can be seen that to the calcium silicate slag base gum filler of the present invention compared with R1 ', R2 ', B1 respectively,
Calcium silicate slag obtained by residue of aluminum-extracted dealkalize is crushed to 600-1500 mesh, is added to as reinforcing agent in rubber formulation, can be carried
Disruptive force, fracture tensile strength and the tearing elongation of high rubber.By R1 and R2 ' compared with as can be seen that by silico-calcium
Decline to a great extent on the contrary to the reinforcing effect of rubber when slag is ground to 3500 mesh, this is probably since powder is meticulous, can cause its ratio
Surface area is excessive, powder reuniting easily occurs in the case of surface energy is very high, therefore not crushing is more thin more is beneficial to rubber
Reinforcement.By R1 as can be seen that the calcium silicate slag base gum filler using the present invention is added to rubber as reinforcing agent compared with B2
In dispensing, there is the reinforcing effect suitable with white carbon.
Wherein, the particle diameter of the calcium silicate slag base gum filler of R1-R3 is respectively 1000,800,1200 mesh, its strengthening action compared with
It is good.R1 can be carried further compared with R4 and R5 as can be seen that when the particle diameter of calcium silicate slag is 800-1200 mesh respectively
The strengthening action of high calcium silicate slag base gum filler；By R1 as can be seen that the concentration of sodium hydroxide solution is 60- compared with R6
100g/L, can further improve the strengthening action for the calcium silicate slag base gum filler being prepared；Can compared with R7 by R1
To find out, the condition of dealkalize processing includes：Temperature is 130-180 DEG C, time 1-1.5h, liquid-solid ratio 4-5, can be further
Improve the strengthening action for the calcium silicate slag base gum filler being prepared.
The calcium silicate slag base gum filler of the present invention, has the reinforcing effect suitable with white carbon, can make the rubber of preparation
Product has higher disruptive force, fracture tensile strength, tearing elongation etc., rubber is had practical value；And this hair
Bright calcium silicate slag base gum filler, preparation process is simple, derives from a wealth of sources, cheap, can significantly reduce the system of rubber
Make cost.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (18)
1. a kind of calcium silicate slag, it is characterised in that the main component of the calcium silicate slag is Si and Ca, also containing a small amount of Al, with silico-calcium
On the basis of the gross weight of slag, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-40 weight %,
The content of CaO is 35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-0.9.
2. calcium silicate slag according to claim 1, wherein, the main thing of the calcium silicate slag is mutually tobermorite.
3. a kind of calcium silicate slag base gum filler, it is characterised in that the filler contains the calcium silicate slag that particle diameter is 600-1500 mesh, described
The main component of calcium silicate slag is Si and Ca, also containing a small amount of Al, on the basis of the gross weight of calcium silicate slag, Si, Ca, Al element point
Not with SiO2、CaO、Al2O3Meter, SiO2Content be that the content of 35-40 weight %, CaO is 35-40 weight %, Al2O3Content
Molar ratio for 1-6 weight %, Ca/Si+Al is 0.7-0.9.
4. calcium silicate slag base gum filler according to claim 3, wherein, the particle diameter of the calcium silicate slag is 800-1200 mesh.
5. calcium silicate slag base gum filler according to claim 3, wherein, the main thing of the calcium silicate slag is mutually snow silico-calcium
Stone.
A kind of 6. preparation method of the calcium silicate slag described in claim 1, it is characterised in that the described method includes：By aluminum-containing mineral
Or the alkaline process residue of aluminum-extracted of waste residue carries out dealkalize processing in lye, wherein, the lye is sodium carbonate, industrial caustic soda, industry
The solution of at least one of weight alkali, calcium hydroxide and lime.
7. according to the method described in claim 6, wherein, aluminum-containing mineral or waste residue are flyash.
8. according to the method described in claim 6, wherein, the lye is sodium hydroxide solution.
9. according to the method described in any one in claim 6-8, wherein, the condition of the dealkalize processing includes：Lye is dense
It is 100-200 DEG C, time 0.5-2h to spend for 20-100g/L, temperature, and it is 3-6, pressure 0.1-1.5MPa that liquid, which consolidates mass ratio,.
10. according to the method described in claim 9, wherein, the concentration of lye is 60-100g/L.
11. according to the method described in claim 9, wherein, the temperature is 130-180 DEG C.
12. according to the method described in claim 9, wherein, the time is 1-1.5h.
13. according to the method described in claim 9, wherein, it is 4-5 that the liquid, which consolidates mass ratio,.
14. according to the method described in claim 9, wherein, the pressure is 0.27-1.0MPa.
A kind of 15. preparation method of calcium silicate slag base gum filler, it is characterised in that the described method includes：Calcium silicate slag is crushed to
600-1500 mesh, wherein, the main component of the calcium silicate slag is Si and Ca, also containing a small amount of Al, with the gross weight of calcium silicate slag
On the basis of, Si, Ca, Al element are respectively with SiO2、CaO、Al2O3Meter, SiO2Content be 35-40 weight %, CaO content be
35-40 weight %, Al2O3Content be that the molar ratio of 1-6 weight %, Ca/Si+Al is 0.7-0.9.
16. according to the method for claim 15, wherein, the main thing of the calcium silicate slag is mutually tobermorite.
17. the method according to claim 15 or 16, wherein, calcium silicate slag is crushed to 800-1200 mesh.
18. calcium silicate slag base gum filler prepared by the method in claim 15-17 described in any one.
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| CN101966999B (en) * | 2010-11-11 | 2012-11-21 | 中国地质大学（北京） | Method for extracting aluminum oxide and white carbon black through two-step alkaline leaching method by adopting high-alumina fly ash |
| CN102897809A (en) * | 2012-11-06 | 2013-01-30 | 大唐国际发电股份有限公司 | Method and equipment for separating and washing fly ash calcium silicate slag |
| EP2927199B1 (en) * | 2012-11-27 | 2022-07-20 | China Energy Investment Corporation Limited | Method for preparing soda-lime-silica glass basic formula and method for extracting aluminum from fly ash for co-production of glass |
| CN103708478B (en) * | 2013-12-30 | 2015-11-25 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | A kind of preparation method of tobermorite |
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