CN106478987A - A kind of waste stone dust surface modifying method based on dry grinding - Google Patents
A kind of waste stone dust surface modifying method based on dry grinding Download PDFInfo
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- CN106478987A CN106478987A CN201610922816.9A CN201610922816A CN106478987A CN 106478987 A CN106478987 A CN 106478987A CN 201610922816 A CN201610922816 A CN 201610922816A CN 106478987 A CN106478987 A CN 106478987A
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- stone dust
- waste stone
- waste
- method based
- surface modifying
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- 239000002699 waste material Substances 0.000 title claims abstract description 90
- 239000004575 stone Substances 0.000 title claims abstract description 77
- 239000000428 dust Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000009837 dry grinding Methods 0.000 title claims abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- 239000011737 fluorine Substances 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 238000003801 milling Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 34
- 239000004579 marble Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 7
- 239000010438 granite Substances 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- -1 rare earth Nitrate Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- 239000011435 rock Substances 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 27
- 238000012986 modification Methods 0.000 abstract description 27
- 238000007385 chemical modification Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000000945 filler Substances 0.000 abstract description 5
- 230000004913 activation Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a kind of waste stone dust surface modifying method based on dry grinding, adding waste stone dust first can finely in the milling apparatus of temperature control, add the ethanol solution of rare earth nitrades, 2～3h is ground under 30～50 DEG C of grinding temperature, then anionic fluorine surfactant is added, 1h is ground under 30～50 DEG C of grinding temperature, finally collect the ultra-fine waste stone dust after grinding.The inventive method is by mechanical-chemical modification, rare-earth surface modification and fluorine surfactant surface modification to combination, jointly surface modification is carried out to waste stone dust, obtained ultra-fine waste stone dust surface-active is high, can be used as the filler of macromolecular material, has widened the application of waste stone dust.
Description
Technical field
The invention belongs to field of material surface modification, is related to a kind of waste stone dust surface modifying method, more particularly to a kind of base
Waste stone dust surface modifying method in dry grinding.
Background technology
Waste stone dust is the discarded object produced in stone machining processing, and which recycles an always difficult problem, and at present, waste stone dust is
Through having obtained some applications in fields such as concrete, mortar, artificial stones, but for the generation total amount of waste stone dust, still not
Whole waste stone dust can be digested completely, the accumulation of a large amount of waste stone dust is caused, how efficient utilization waste stone dust is a urgent need to resolve
Environment and social concern.After waste stone dust is processed as applying filler in macromolecular material, can prepare polymer-based
Composite, has widened the range of application of waste stone dust, advantageously accounts for its application problem.But waste stone dust belongs to inorganic particle,
Which is poor with the compatibility of high-molecular organic material, and surface adhesion is weak, easily causes the decline of composite materials property, so
Need to carry out which surface modification to improve its compatibility with macromolecule matrix material.
At present, the method for Surface Modification of Inorganic Powder mainly has surface to cover modification, local chemical modification, mechanical force and chemical
Modification, outer layer membrane modifying, high-energy surface are modified and carry out surface modification etc., wherein mechanical-chemical modification using precipitation reaction
Refer to strengthen the surface-active of particle by the method such as crushing, grinding, rub, make with strongly active powder surface and other things
Matter is reacted, is adhered to, and reaches the purpose of surface modification.Mechanical force and chemical surface modification combines ultra-fine grinding and surface modification
Together, save time, saving of labor, save energy consumption, easy to operate, with vast potential for future development.
By waste stone dust using mechanical-chemical modification method carry out surface modification can reach crushing and surface modification dual
Purpose, but single modification by mechanical force still can not efficiently improve the compatibility of waste stone dust and macromolecular material, can be in conjunction with adopting other
Surface modifier, plays synergy, reaches the efficient surface to waste stone dust modified.Fluorine surfactant is special surface activity
One class of agent, modified effect are good, are replaced by fluorine atoms the hydrogen moiety in the hydrocarbon chain of conventional surfactants or all
Afterwards, the surfactant with carbon fluorine chain hydrophobic group is referred to as fluorine surfactant, due to the presence of fluorine, fluorine surfactant surface
Activity is high, while having the characteristics such as dispersion, wetting.While rare earth ion is also a kind of surface modifier, which has stronger network
Conjunction ability, has stronger coordination to fluorine plasma, forms chemical bond, plays the effect of surface modification.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, a kind of waste stone dust surface modifying method, Yi Zhongji is provided
In the waste stone dust surface modifying method of dry grinding, the method process is simple, by mechanical-chemical modification, rare-earth surface modification and
Fluorine surfactant surface modification carries out surface modification, obtained ultra-fine waste stone dust surface-active jointly to combination to waste stone dust
Height, can be used as the filler of macromolecular material, widen the application of waste stone dust.
For realizing object above, the technical solution used in the present invention is：
A kind of waste stone dust surface modifying method based on dry grinding, comprises the following steps：
(1) adding waste stone dust can finely in the milling apparatus of temperature control, the ethanol solution of addition rare earth nitrades, in 30～
2～3h is ground under 50 DEG C of grinding temperature；
(2) anionic fluorine surfactant is added, under 30～50 DEG C of grinding temperature, grinds 1h；
(3) the ultra-fine waste stone dust after grinding is collected.
The waste stone dust is waste marble powder, one or two mixture of the granite stone powder that gives up.
The rare earth nitrades are lanthanum nitrate, one kind of cerous nitrate.
The addition of the rare earth nitrades is the 0.5～2% of the waste stone dust weight.
The anionic fluorine surfactant is sulfonate type fluorine surfactant, sulfuric ester salt form fluorine surface-active
Agent, one kind of phosphate salt form fluorine surfactant.
The addition of the anionic fluorine surfactant is the 0.5～1% of the waste stone dust weight.
The particle size range of the ultra-fine waste stone dust is 1000～1200 mesh.
The present invention by mechanical-chemical modification, rare-earth surface modification and fluorine surfactant surface modification to combination, jointly
Surface modification is carried out to waste stone dust, surface active is carried out to waste stone dust first with mechanical-chemical modification method, while reaching
The purpose of ultra-fine grinding, through processing, surface-active is improved waste stone dust, and surface hydroxyl increases, and hydroxyl can be with rare earth ion network
Conjunction forms chemical bond, is subsequently adding anionic fluorine surfactant, and rare earth ion is strong with the complexing power of fluorine, can set up relatively
Strong chemical bond, is thus formed a complex compound network on waste stone dust surface, can improve and especially be contained with macromolecular material
The adhesion of fluoropolymer, makes waste stone dust can be used as the filler of polymer-based composite.
Beneficial effects of the present invention：
(1) present invention is by mechanical-chemical modification, rare-earth surface modification and fluorine surfactant surface modification to combination, common
Surface modification is carried out with to waste stone dust, modified effect is good, the compatibility of waste stone dust and macromolecule matrix material can be effectively improved, increase
Plus both adhesions；
(2) present invention carries out surface modification using mechanical-chemical modification method to waste stone dust, can reach surface work simultaneously
Change the dual purpose with ultra-fine grinding；
(3) collective effect of rare earth ion and fluorine surfactant can form a complex compound network on waste stone dust surface,
The adhesion of its especially fluoropolymer with macromolecular material can be improved, makes waste stone dust can be used as polymer-based composite
Filler；
(4) the inventive method process is simple, during dry grinding is carried out, synchronously adds rare-earth modifier and fluorine table
Face activating agent, is not required to increase processing step.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but does not limit protection scope of the present invention.
Embodiment 1
A kind of waste stone dust surface modifying method based on dry grinding, comprises the following steps：
(1) adding waste marble powder can finely in the milling apparatus of temperature control, the ethanol solution of addition lanthanum nitrate, lanthanum nitrate
Addition be the 1% of waste stone dust weight, grind 3h under 30 DEG C of the grinding temperature；
(2) sulfonate type fluorine surfactant is added, and its addition is the 0.5% of waste stone dust weight, in 30 DEG C grind
1h is ground at a temperature of mill；
(3) collect the ultra-fine waste marble powder after grinding, the particle size range of ultra-fine waste marble powder for 1000～
1200 mesh.
In order to verify embodiment 1 prepare surface modification after ultra-fine waste marble powder performance, carried out activation grade, suction
Oil value and the test of settling volume, activation grade can reflect the surface modification effect of waste marble powder, and the higher explanation of activation grade is modified
Agent is bigger to the cladding degree of waste marble powder, and activation effect is better；Oil factor is with the consumption of dibutyl phthalate (DOP)
To react the quality of waste stone dust modified effect, oil factor then illustrates that greatly waste marble powder filled high polymer material can absorb more
The auxiliary agents such as plasticizer, cause processing cost to increase, and general, oil factor is the smaller the better；Settling volume can reflect waste marble powder
Dispersiveness in a liquid, if waste marble powder good dispersion in atoleine, atoleine has preferably profit to powder
Moist, powder is difficult aggregation and bonding, and in sedimentation, particle arrangement is piled up closely, and settling volume is less.If conversely, dispersiveness
Poor, then powder is easy to aggregation, leaves because of bridging compared with concrete dynamic modulus, easily form loose deposit during sedimentation between powder, sedimentation
Volume is larger.Method of testing is as follows：
(1) activation grade：Ultra-fine for a certain amount of embodiment 1 waste stone dust is added in suitable quantity of water, glass bar stirs 2min, stand 1h
Afterwards, the floating thing on upper strata is taken out, drying is weighed, calculates activation grade according to the following formula：Activation grade=(floating thing weight/gross mass) ×
100%,
(2) oil factor：Accurately weigh ultra-fine waste stone dust to be placed on glass plate, DOP is instilled with buret to ultra-fine waste stone dust,
It is stirred with clean glass bar in dropping, when so that sample is just all glued by glass bar, writes down O-phthalic
The consumption of dibutyl phthalate, calculates oil factor according to the following formula：Oil factor (mL/g)=DOP volume/waste stone dust quality,
(3) settling volume：Measure 20mL atoleine to add in graduated cylinder with a scale, ultra-fine for 2g waste stone dust is added to
In 20mL atoleine, 3min is shaken with the speed of 100～120 times per minute, 24h is stood, record solid volume is and settles
Volume.
Test result shows：The activation grade of ultra-fine waste marble powder obtained in embodiment 1 is 98.1%, and oil factor is
0.065mL/g, settling volume are 0.7mL；And be 74.8% without the activation grade of the modified waste marble powder of 1 method of embodiment,
Oil factor is 0.170mL/g, and settling volume is 3.0mL；Knowable to analyze data, ultra-fine waste marble powder obtained in embodiment 1
Activation grade is significantly increased, and oil factor and settling volume all decline substantially, illustrates that 1 method of embodiment changes to the surface of waste marble powder
Property effect is good, can improve dispersiveness and compatibility of the waste marble powder in atoleine, further illustrates embodiment 1 and gives up Dali
Stone flour is can be applicable in macromolecular material, with good compatibility.
Embodiment 2
A kind of waste stone dust surface modifying method based on dry grinding, comprises the following steps：
(1) adding waste marble powder can finely in the milling apparatus of temperature control, the ethanol solution of addition lanthanum nitrate, lanthanum nitrate
Addition be the 1% of waste stone dust weight, grind 2h under 40 DEG C of the grinding temperature；
(2) sulfuric ester salt form fluorine surfactant is added, and its addition is the 1% of waste stone dust weight, in 40 DEG C grind
1h is ground at a temperature of mill；
(3) collect the ultra-fine waste marble powder after grinding, the particle size range of ultra-fine waste marble powder for 1000～
1200 mesh.
Test result shows：The activation grade of ultra-fine waste marble powder obtained in embodiment 2 is 98.9%, and oil factor is
0.055mL/g, settling volume are 0.4mL, and modified effect is good.
Embodiment 3
A kind of waste stone dust surface modifying method based on dry grinding, comprises the following steps：
(1) adding useless granite stone powder can finely in the milling apparatus of temperature control, the ethanol solution of addition cerous nitrate, nitric acid
The addition of cerium is the 1% of waste stone dust weight, grinds 3h under 30 DEG C of grinding temperature；
(2) phosphate salt form fluorine surfactant is added, and its addition is the 0.5% of waste stone dust weight, in 30 DEG C
1h is ground under grinding temperature；
(3) the ultra-fine useless granite stone powder after grinding is collected, and the particle size range of ultra-fine useless granite stone powder is 1000
～1200 mesh.
Test result shows：The activation grade of ultra-fine useless granite stone powder obtained in embodiment 3 is 98.3%, and oil factor is
0.068mL/g, settling volume are 0.6mL, and modified effect is good.
Above-described embodiment is only one of presently preferred embodiments of the present invention, is not limited the scope of the invention with this, therefore：
The equivalence changes done by all structures under this invention, shape, principle, all should be covered by within protection scope of the present invention.
Claims (7)
1. a kind of waste stone dust surface modifying method based on dry grinding, it is characterised in that comprise the following steps：(1) by barren rock
Powder is added can finely in the milling apparatus of temperature control, and the ethanol solution of addition rare earth nitrades, under 30～50 DEG C of grinding temperature
2～3h of grinding；(2) anionic fluorine surfactant is added, under 30～50 DEG C of grinding temperature, grinds 1h；(3) collect
Ultra-fine waste stone dust after grinding.
2. the waste stone dust surface modifying method based on dry grinding according to claim 1, it is characterised in that the barren rock
Powder is waste marble powder, one or two mixture of the granite stone powder that gives up.
3. the waste stone dust surface modifying method based on dry grinding according to claim 1, it is characterised in that the rare earth
Nitrate is lanthanum nitrate, one kind of cerous nitrate.
4. the waste stone dust surface modifying method based on dry grinding according to claim 1, it is characterised in that the rare earth
The addition of nitrate is the 0.5～2% of the waste stone dust weight.
5. the waste stone dust surface modifying method based on dry grinding according to claim 1, it is characterised in that described cloudy from
Subtype fluorine surfactant is sulfonate type fluorine surfactant, sulfuric ester salt form fluorine surfactant, phosphate salt form fluorine table
One kind of face activating agent.
6. the waste stone dust surface modifying method based on dry grinding according to claim 1, it is characterised in that described cloudy from
The addition of subtype fluorine surfactant is the 0.5～1% of the waste stone dust weight.
7. the waste stone dust surface modifying method based on dry grinding according to claim 1, it is characterised in that described ultra-fine
The particle size range of waste stone dust is 1000～1200 mesh.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610922816.9A CN106478987B (en) | 2016-10-24 | 2016-10-24 | A kind of waste stone dust surface modifying method based on dry grinding |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610922816.9A CN106478987B (en) | 2016-10-24 | 2016-10-24 | A kind of waste stone dust surface modifying method based on dry grinding |
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| Publication Number | Publication Date |
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| CN106478987A true CN106478987A (en) | 2017-03-08 |
| CN106478987B CN106478987B (en) | 2018-07-03 |
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| CN108178563A (en) * | 2018-01-17 | 2018-06-19 | 福建弘高石粉综合利用有限公司 | A kind of high performance superfine sand concrete material preparation method containing waste stone dust |
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| CN108178563A (en) * | 2018-01-17 | 2018-06-19 | 福建弘高石粉综合利用有限公司 | A kind of high performance superfine sand concrete material preparation method containing waste stone dust |
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