CN102732063A - Modified fly ash, preparation method thereof, and preparation apparatus thereof - Google Patents
Modified fly ash, preparation method thereof, and preparation apparatus thereof Download PDFInfo
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Abstract
The invention provides a preparation method of modified fly ash. In a sealed negative-pressure system, fly ash is adopted as a raw material. When winnowing grading processing is carried out upon the fly ash particles, the graded fine particles and ultra-fine particles are subjected to a chemical-spraying surface modification treatment; the obtained products are heated and dried, such that a target product of the modified fly ash is obtained. According to the modified fly ash provided by the invention, one or more saturated-structure or unsaturated-structure organic groups are bonded on the surfaces of the particles, and an activation index is higher than 0.9. The invention also discloses a fly ash sorting and modifying apparatus. The technical method provided by the invention is energy-saving and environment-friendly, and is advantaged in high utilization rate of fly ash. The obtained modified fly ash is advantaged in wide particle fineness selection range, small dosage of a coupling agent, uniform distribution of the coupling agent, good adaptability with polymer substrates, and the like. In rubber product filling, the modified fly ash can be used for completely replacing calcium carbonate and powdered steatile, or partially replacing carbon black. The modified fly ash is a renewable resource material with low cost and high quality.
Description
Technical field
The present invention relates to rubber item filler processing technique field, relate to a kind of preparation modified coal ash, its classification and surface treatment method and implement device particularly.
Background technology
Flyash is the solid waste that coal-fired station discharges, the dispersion system of being made up of the particulate of different structure and form.The main chemical compositions of flyash is silicon, aluminium, ferriferous oxide, a certain amount of calcium, magnesium, oxysulfide, the copper of trace, chromium, lead etc., and unburnt carbon granule.The flyash whole nation year total emission volumn surpasses 100,000,000 tons, and wherein obtain utilizing be less than 50%, a large amount of flyash are piled up in ash, land occupation resource not only, and water quality and environment polluted.Undressed flyash can only be used as the building materials raw material, and like cement filler or fragment of brick etc., economic worth is not high.So, add the comprehensive development and utilization of strength fly-ash, improve its economic benefit and added value, no matter see from environmental protection, angle energy-conservation or resource reutilization, all be very necessary.
Owing to compositions such as the silicon-dioxide that contains a large amount of stable performances in the flyash, aluminum oxide, red stone; The particle surface of inorganic hydrophilic property; Poor with the consistency of hydrophobicity organic matrixs such as rubber, be prone to make the bonding surface of particle and matrix to become the weak link of matrix material; In addition, the surface energy of flyash is higher, and fine size is easy to generate reunion, is difficult in homodisperse in the rubber matrix, and its range of application is restricted, and result of use is had a greatly reduced quality.Therefore, must improve its surface texture.Flyash is after the coupling agent surface-treated, and hydrophobicity strengthens, and dispersion stabilization improves, and has extensive use at the aspects such as filler of organic materials.Up to now, develop multiple coupling agents such as silane, aluminic acid ester, titanic acid ester, zirconate, be used for the surface chemical modification of flyash.For example; Chinese patent CN 101240095A, 1047272,102070794A, 102010535A etc. disclose and have utilized coupling agent that flyash is carried out surface-treated; Used properties-correcting agent is many to be main with silane coupling agent, is auxilliary to help properties-correcting agent, perhaps selects dedicated modified dose of flyash for use.What modified effect was best is some organosilane, secondly is metal organic acid ester class coupling agents such as aluminium, titanium, cobalt, and for using two or more metal organic acid ester class coupling agents, composite through suitably, synergy can meet or exceed organosilane.Patent CN 101348578 utilizes hydrofluoric acid as etching reagent corrosion treatment to be carried out on the flyash surface, after activated again dose activation, nano modification, coupling agent grafting hydrophobicity etc. are handled, obtains fly ash micro-sphere rubber filling.Patent CN 1880385A heats flyash and dewaters, screens, after grinding etc. handles, is used for plastic and rubber filler.The defective of prior art is that properties-correcting agent directly adds in product of rubber and plastic is produced; Consumption is big; At the particle surface skewness, the process of lapping energy consumption is high, particle is not spherical in shape and sharp cutting edge is arranged, and the red stone residual quantity is big; And production technique or processing units poor sealing cause that fine particle waves etc. in atmosphere; Thereby influence the effect of its filling and the outward appearance and the quality of goods,, and seriously restricted the large-scale production of modified coal ash and promoting the use of in rubber industry like degradation under rubber surface bloom, the mechanical strength.The method and apparatus of, nano particles stage extraction little like the disclosed flyash of patent CN 1156334C, but still do not solve the problem of fly ash grain surface-treated, still influence it and in rubber and plastic, directly add the effect of using.
Summary of the invention
The objective of the invention is to, overcome the above defective of prior art, a kind of preparation method of modified coal ash is provided, is raw material with flyash, handles through selection by winnowing classification and surface spray chemical modification integral process, makes modified coal ash.The modified coal ash that the inventive method makes is as loading material of rubber, can all replace light calcium carbonate, talcum powder, Namigai or part and replace carbon black and be filled in the rubber item.
The invention provides a kind of preparation method of modified coal ash; In airtight negative pressure system; With flyash is raw material; When said fly ash grain is carried out the selection by winnowing stage treatment, fine particle and the fines that sub-elect are carried out the processing of spray surface chemical modification, after heating, drying, obtain purpose product modified coal ash.
Among the present invention, said fine grain particle diameter is more than 800 orders; The particle diameter of said ultra-fine grain is more than 1000 orders; The particle diameter of said fines is more than 3000 orders.
Among the present invention, said selection by winnowing classification is in the size separation equipment of airtight negative pressure, to carry out; Said size separation equipment comprises first step separator, second stage separator, third stage separator.
Among the present invention, said selection by winnowing classification is through the wind-force size of switching rotational gas flow and regulating every grade of separator, in first step separator, tells coarse particles, in the separator of the second stage, tells fine particle, in third stage separator, tells fines.
Among the present invention; It is in second stage separator and third stage separator, to carry out that said spray surface chemical modification is handled, by being arranged at least one shower nozzle in said second stage separator and the third stage separator to said fine particle and fines surperficial direct spraying modified dose.
Among the present invention, further, will in said fine particle after said spray surface chemical modification is handled and fines importing kneader, stir, kneading and heat treated, the strengthening surface coupling.
Among the present invention, at said kneader top at least one shower nozzle is set further.
Among the present invention, surface chemical modification is meant that the flyash surface is rich in oh group, they can with coupling agent such as monoalkoxy fatty acid type titanate coupling agent [i-C
3H
7OTi (OCOR)
3] in close inorganic phase (short carbon chain alkyl) the chemically bonded effect takes place, bag is attached to the fly ash grain surface, between mineral filler and organic polymer, forms chemical bridged bond, makes coupling agent have surface modification effect.Its coupling mechanism is as follows:
Among the present invention, said properties-correcting agent is the vaporific dispersion liquid of coupling agent.Said coupling agent is any one or two or more mixing of silane, aluminic acid ester, titanic acid ester, zirconate; Its consumption is the 0.2-3% of said flyash weight.Said dispersion liquid is any one or two or more mixing of solvent oil, alcohol, trolamine, epoxy soybean oil, allyloxy propylene oxide, glycidyl ether; Its consumption is the 0.5-5% of said flyash weight.
Further, in the separator of the said second stage, the further sorting of fine particle more than said 800 orders is obtained ultra-fine grain; The particle diameter of said ultra-fine grain is 1200 orders or 2000 orders.
Among the present invention, further from said coarse particles, obtain the magnet raw material through magnetic selection method.
The modified coal ash that the present invention also provides a kind of preparation method according to claim 1 to prepare; One or more organic groups saturated or unsaturated structure of its particle surface chemically bonded; Activation index is very high, and activation index is very tall and big in 0.9, and hydrophobicity is strong; And consistency is good between the organic polymer, can be used as the stopping composition of rubber item.
The present invention also provides a kind of coal ash sorting and reforming apparatus, and under airtight negative pressure state, this device is specifically designed in the sorting fly ash grain this particle surface is carried out modification.Said device comprises the size separation equipment that is used for the sorting fly ash grain and is arranged on the top of size separation equipment and/or at least one shower nozzle all around that this shower nozzle is used for directly spraying chemical modifier to the surface of the fly ash grain of size separation equipment.
Coal ash sorting of the present invention and reforming apparatus are used in the sorting fly ash grain, this particle surface being carried out modification, comprising: the blower fan and the air pump of first step separator, second stage separator, third stage separator, different capacity (0.5-100 kilowatt); And being distributed at least one shower nozzle in said second stage separator and the third stage separator, it is arranged on the top of size separation equipment and/or all around, is used for to the surface of the fly ash grain of size separation equipment directly spraying modified dose; And the kneader or the impeller that are tightly connected with said second stage separator and third stage separator respectively, be used to strengthen the Chemical bond of coupling agent and particle surface and the effect of coupled action.
Compared with prior art, beneficial effect of the present invention comprises: the selection by winnowing classification of flyash is in the negative pressure system of Sealing Arrangement, to carry out, and no dust waves in atmosphere, need not the milled processed of high energy consumption, is a kind of production technique of energy-conserving and environment-protective.Flyash after adopting spray art to the selection by winnowing classification carries out surface chemical modification to be handled; And these two important steps are handled in selection by winnowing classification and modification be integrated in the equipment and carry out; Realize classification and the integrative coordinated operation of modification; Can optimizing equipment, can make coupling agent be dispersed in particle surface again, for reducing the coupling agent consumption, satisfying coupling and filling effect provides assurance.Adopt the close-coupled processing modified coal ash that obtains of selection by winnowing classification of the present invention and surface spray chemical modifying process, turnout is big, can reach the industrial scale of kiloton to ton, has the demonstration effect and the promotional value of industrial application.
Through regulating the wind-force size flyash is carried out the selection by winnowing classification, the level that can obtain multiple ultra-fine granularity is divided, and can satisfy the demand of the rubber item of different sorts and quality to stopping composition.The modified coal ash that the present invention makes is particularly suitable for the stopping composition as high-quality rubber items such as cables, can substitute light calcium carbonate, nano-calcium carbonate or talcum powder.In addition; After a modification is handled through the superfine granularity of the resulting flyash of selection by winnowing classification (more than 3000 orders or below 4 microns) level branch process; Can partly substitute carbon black, it has strengthening action as stopping composition to rubber item, has greatly improved the economic worth of flyash.
Among the present invention, when flyash was carried out the selection by winnowing classification, the coarse particles that at first will influence filling effect separated with martial ethiops and is collected in first grade branch, reaches the purpose of promoting what is beneficial and abolish what is harmful.Coarse particles can be used for the manufacturing of building block, and martial ethiops can directly be used for the magnetic stopping composition of product of rubber and plastic, or further obtains high-grade magnet raw material through magnetic separation, greatly promotes its added value, really accomplishes to make the best use of everything, turn waste into wealth.
Description of drawings
Fig. 1 is preparing method's of the present invention process flow diagram.
Embodiment
In conjunction with following specific embodiment and accompanying drawing, the present invention is done further explain, protection content of the present invention is not limited to following examples.Under spirit that does not deviate from inventive concept and scope, variation and advantage that those skilled in the art can expect all are included among the present invention, and are protection domain with the appending claims.The process of embodiment of the present invention, condition, reagent, experimental technique etc. except that the following content of mentioning specially, are the universal knowledege and the common practise of this area, and the present invention does not make special limiting content.
Preparing method of the present invention, the selection by winnowing classification and the surface spray chemical modifying process of superfined flyash (can be used as loading material of rubber) is integrated.In the inventive method; Flyash carries out the selection by winnowing classification according to granulometric composition, density and particle diameter are different in the negative pressure system of Sealing Arrangement, collect the ultra-fine grain of the coarse particles that obtains being rich in red stone, 800 order fine particles (18 microns of particle diameters) to 2000 orders (6.5 microns of particle diameters) respectively and a plurality of grades of branches such as fines of (particle diameter is below 4 microns) more than 3000 orders; Metering shower nozzle by being installed on pneumatic separator or the kneader directly sprays the vaporific dispersion liquid of coupling agent to particle surface, makes the surface-treated of flyash and gradation accomplish synchronously; Through stirring, kneading and heat treated, the strengthening surface coupling effect, again in pipeline through hot blast or microwave drying, remove anhydrate, odor component such as dispersion liquid, obtain superfine modified flyash product.
Detailed process of the present invention is: the selection by winnowing classification of flyash is carried out in the negative pressure system of Sealing Arrangement; Through rotational gas flow switching, every grade of separator inner blower power is that rotating speed changes and secondary wind-force size adjustment; Different according to granulometric composition, density and particle diameter, collect the above fines (accounting for the 10-15% of former flyash weight) of coarse particles (accounting for the 15-50% of former flyash weight), 800 order to 2000 purpose fine particles (accounting for the 40-70% of former flyash weight) and 3000 orders that obtain being rich in red stone respectively.The surface spray chemical modification of flyash, by the top that is installed in second stage pneumatic separator, third stage pneumatic separator and around different angles or a plurality of metering shower nozzles of being installed in the kneader top directly spray the vaporific dispersion liquid of coupling agent to particle surface and realize.Particle surface modification process and selection by winnowing classification process are synchronous completion.After the coupling of surface; With the flyash of variable grain fineness respectively through stirring, kneading and heat treated; For example, imported in the kneader in 50-100 ℃ of heat treated 5-30 minute, again in pipeline through hot blast, infrared, electromagnetism or micro-wave drying; Remove anhydrate, odor component such as dispersion liquid, obtain the modified coal ash PM for particulate matter that surperficial coupled action effect is reinforced.Cooling back packing obtains high-quality or has the superfined flyash rubber filler product of half strengthening action.
Chemical modifier among the preparation method of the present invention is the vaporific dispersion liquid of coupling agent, and wherein, coupling agent comprises that in silane, aluminic acid ester, titanic acid ester, the zirconate one or more are compound.Dispersion liquid comprises one or more mixing in solvent oil, alcohol, ETHYLE ACETATE, trolamine, epoxy soybean oil, allyloxy propylene oxide, the glycidyl ether.
Among the preparation method of the present invention, the process reform through rotational gas flow switches and wind-force is regulated can also segment in the separator of the second stage, and obtain the fine particle or the ultra-fine grain of a plurality of grades of branches such as 800 orders, 1200 orders or 2000 orders respectively.
The modified coal ash that the inventive method makes; Its particle fineness range of choice wide (more than 800 order to 3000 orders); One or more organic groups saturated or unsaturated structure of particle surface chemically bonded, hydrophobicity strong (activation index is greater than 0.9) is good with the polymeric matrix consistency; Disperse and the stability in storage height, be suitable for the especially filling of rubber item of polymkeric substance.
The modified coal ash that makes with the inventive method makes rubber item as loading material of rubber, and its prescription is: rubber 15-20 part, modified coal ash 10-30 part; Carbon black 2-6 part, Natural manganese dioxide 2-5 part, paraffin 0.5-1 part, trioctyl trimellitate 2-4 part; Rubber oil 0.5-1 part, Di Cumyl Peroxide 99 0.5-1 part, triallyl isocyanurate 0.3-0.6 part; Zinc oxide 0.5-1 part, Triple Pressed Stearic Acid 0.2-0.5 part, anti-aging agent 0.2-0.5 part.
In the above-mentioned prescription, said rubber is: one or more mixing in chlorinated polyethylene rubber, tree elastomer, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, X 050, butyl rubber, paracril, polyisoprene rubber, the ethylene-propylene diene copolymer.
In the above-mentioned prescription, the modified coal ash that the inventive method makes is: one or more mixing of 800 orders, 1200 orders, 2000 orders or 3000 order fly ash grains.
Embodiment 1
As shown in Figure 1, the flyash in the flyash storage tank is sent in the gas feed mixer with pressurized air, under the suction function of induced draft fan, fly ash grain imports the rotational gas flow separator through pipeline with airflow, in the negative pressure system of Sealing Arrangement, carries out the selection by winnowing classification.The rotational gas flow separator comprises first step separator, second stage separator, third stage separator.
Switch air-flow, the less suction force of control blower fan descends coarse particles spiral in first step separator, discharges and be stored in the container (account for former grey weight 15%) through drain.This coarse particles is that the level that is rich in martial ethiops is divided, and can directly be used as the magnetic stopping composition, or further obtain high-grade magnet raw material through magnetic separation.
Control the bigger suction force of blower fan at the corresponding levels; The above fine particle of 800 orders gets into that spiral descends in the separator of the second stage (account for former grey weight 70%); Directly spray the vaporific dispersion liquid of coupling agent (flyash per ton is with 5 kilograms the silane coupling agent and the mixed solution of titanate coupling agent and 5 kilograms of solvent oil and epoxy soybean oil) to the fine particle surface synchronously by a plurality of metering shower nozzles that are installed in winnowing machine top, the second stage and different angles on every side; And in the entering kneader in 80 ℃ of heat treated 15 minutes, again in pipeline through warm air drying, cooling back packing; Obtain purpose product modified coal ash, can be used as the rubber filler product.
Simultaneously; The above fines of 3000 orders get into that spiral descends in the third stage separator (account for former grey weight 15%); Directly spray the vaporific dispersion liquid of coupling agent (flyash per ton is with 20 kilograms the silane coupling agent and the mixed solution of titanate coupling agent and 20 kilograms of solvent oil and epoxy soybean oil) to the fines surface synchronously by a plurality of metering shower nozzles that are installed in third stage winnowing machine top and different angles on every side; And in the entering kneader in 100 ℃ of heat treated 30 minutes, again in pipeline through warm air drying, cooling back packing; Obtain modified coal ash, can be used as high-quality flyash rubber filler product with half strengthening action.
The modified coal ash that present embodiment makes serves as that main level is divided with the fine particle more than 800 orders, and its surface is covered more complete by coupling agent, can be used for the stopping composition of middle-grade rubber item.The modified coal ash that present embodiment makes, one or more organic groups saturated or unsaturated structure of its particle surface chemically bonded, hydrophobicity is strong, and activation index reaches 0.90.
Embodiment 2
With reference to figure 1; Flyash in the storage tank is sent in the gas feed mixer with pressurized air; Under the suction function of induced draft fan, import the rotational gas flow separator with airflow through pipeline; The suction force of regulating and control blower fan at the corresponding levels is big slightly than corresponding wind-force among the embodiment 1, and coarse particles spiral in first step separator descends, and discharges and be stored in the container (account for former grey weight 30%) through drain.
Reference implementation example 1, further, through rotational gas flow switch and the suction force that keeps blower fan at the corresponding levels and embodiment 1 in corresponding wind-force size basically identical, in the separator of the second stage, segment and obtain the above ultra-fine grain of 1200 orders.The above ultra-fine grain of 1200 orders gets into that spiral descends in the separator of the second stage (account for former grey weight 60%); Directly spray the vaporific dispersion liquid of coupling agent (flyash per ton is with 10 kilograms titanate coupling agent and aluminate coupling agent, 10 kilograms the mixed solution of alcohol, trolamine and allyloxy propylene oxide) to particle surface synchronously by a plurality of metering shower nozzles that are installed in different angles around the winnowing machine top, the second stage; And 100 ℃ of heat treated 20 minutes in the entering kneader; Again in pipeline through micro-wave drying; Cooling back packing obtains modified coal ash, can be used as the rubber filler product.
The above fines of 3000 orders get into that spiral descends in the third stage separator (account for former grey weight 10%); In third stage separator, fines being done modification with same way as handles; Obtain modified coal ash, can be used as high-quality flyash rubber filler product with half strengthening action.The modified coal ash that present embodiment makes, one or more organic groups saturated or unsaturated structure of its particle surface chemically bonded, hydrophobicity is strong, and activation index reaches 0.92.
The modified coal ash that present embodiment makes serves as that main level is divided with the ultra-fine grain more than 1200 orders, and its surface is covered complete by coupling agent, can be used for the stopping composition of medium-to-high grade rubber item.
Embodiment 3
Flyash in the storage tank is sent in the gas feed mixer with pressurized air; Under the suction function of induced draft fan, import the rotational gas flow separator with airflow through pipeline; The suction force of regulating and control blower fan at the corresponding levels is bigger than corresponding wind-force among the embodiment 2; Coarse particles spiral in first step separator descends, and discharges and be stored in the container (account for former grey weight 50%) through drain.
Reference implementation example 1, further, through rotational gas flow switch and the suction force that keeps blower fan at the corresponding levels and embodiment 1 in the processing condition of corresponding wind-force size basically identical, in the separator of the second stage, segment and obtain the above ultra-fine grain of 2000 orders.The above ultra-fine grain of 2000 orders gets into that spiral descends in the separator of the second stage (account for former grey weight 40%); Directly spray the vaporific dispersion liquid of coupling agent (flyash per ton with 15 kilograms zirconium ester coupling agent and aluminate coupling agent, 15 kilograms alcohol and the mixed solution of glycidyl ether) to particle surface synchronously by a plurality of metering shower nozzles that are installed in different angles around the winnowing machine top, the second stage; And in the entering kneader in 80 ℃ of heat treated 30 minutes; Again in pipeline through warm air drying; Cooling back packing obtains modified coal ash, can be used as the rubber filler product.
The above fines of 3000 orders get into that spiral descends in the third stage separator (account for former grey weight 10%); In third stage separator, fines being done modification with same procedure handles; Obtain modified coal ash, can be used as high-quality flyash rubber filler product with half strengthening action.The modified coal ash that present embodiment makes, one or more organic groups saturated or unsaturated structure of its particle surface chemically bonded, hydrophobicity is strong, and activation index reaches 0.93.
In the present embodiment, the modified coal ash that makes serves as that main level is divided with the ultra-fine grain more than 2000 orders, and its surface is covered complete by coupling agent, can be used for the stopping composition of high-grade rubber item.In first step separator, collect 50% the coarse particles that accounts for former grey weight obtain, can also pass through the secondary sorting, obtain the above fine particle product of 800 orders.
Embodiment 4
In the present embodiment, other technological process is identical with embodiment 1-3 with treatment process, directly sprays the vaporific dispersion liquid of coupling agent to particle surface synchronously by a plurality of metering shower nozzles that are installed in the kneader top.
The modified coal ash that present embodiment makes, one or more organic groups saturated or unsaturated structure of its particle surface chemically bonded, hydrophobicity is strong, and activation index reaches 0.91.
Embodiment 5
The preparation rubber item, its prescription is: 16 parts of chlorinated polyethylene rubbers, 21 parts of the modified coal ashs that preparation method of the present invention makes; 3 parts of carbon blacks, 2 parts in Natural manganese dioxide, 0.6 part in paraffin; 2.5 parts of trioctyl trimellitates; 0.8 part of rubber oil, 0.5 part of Di Cumyl Peroxide 99,0.3 part of triallyl isocyanurate.Each material of above-mentioned formula ratio is joined in the mixing roll, in 90 ℃ times mixing 7 minutes, open and refine 2 minutes to sheet, in 170 ℃ of sulfurations 3 minutes, the tensile strength of prepared product was 9.7MPa, and elongation at break is 400%.
As comparing, when being used as stopping composition with unmodified flyash, the tensile strength of its goods is 7.5MPa, and elongation at break is 460%.When being used as stopping composition with talcum powder, the tensile strength of its goods is 8.7MPa, and elongation at break is 420%.
Visible through relatively; The modified coal ash that preparation method of the present invention obtains has increased surface active groups through the modification processing, and consistency and bonding force between flyash and the rubber matrix are increased; Thereby improved the physical and mechanical properties of rubber, had good reinforcing effect.
Embodiment 6
The preparation rubber item, its prescription is: 16 parts of tree elastomers, 30 parts of the modified coal ashs that preparation method of the present invention obtains, 5 parts of carbon blacks, 0.7 part in zinc oxide, 0.2 part in paraffin, 0.2 part of Triple Pressed Stearic Acid, 0.2 part in anti-aging agent.Each material of formula ratio is joined in the mixing roll,, open refining 2 minutes again, be adjusted to the thin slice of 4 millimeters thickness in 90 ℃ times mixing 7 minutes.In temperature is that 180 ℃, pressure are under the 15MPa condition, vulcanizes 2 minutes.The tensile strength of prepared product is 6.9MPa, and elongation at break is 380%.
As comparing, when being used as stopping composition with unmodified flyash, the tensile strength of its goods is 5.5MPa, and elongation at break is 430%.When being used as stopping composition with light calcium carbonate, the tensile strength of its goods is 6.6MPa, and elongation at break is 370%.Relatively more visible, the modified coal ash for preparing by preparation method of the present invention has good strengthening action to tree elastomer.
Claims (11)
1. the preparation method of a modified coal ash; It is characterized in that; In airtight negative pressure system, be raw material with flyash, said fly ash grain is being carried out the selection by winnowing fractionated simultaneously; The fine particle, ultra-fine grain and the fines that the sub-elect chemical modification of spraying is handled, through heating, obtaining said modified coal ash after the drying.
2. the preparation method of modified coal ash according to claim 1 is characterized in that said fine grain particle diameter is more than 800 orders; The particle diameter of said ultra-fine grain is more than 1000 orders; The particle diameter of said fines is more than 3000 orders.
3. the preparation method of modified coal ash according to claim 1 is characterized in that said selection by winnowing classification is in the size separation equipment of airtight negative pressure, to carry out; Said size separation equipment comprises first step separator, second stage separator, third stage separator.
4. like the preparation method of the said superfined flyash of claim 3; It is characterized in that; Said selection by winnowing classification is through switching rotational gas flow and regulating wind-force; In first step separator, tell coarse particles, in the separator of the second stage, tell fine particle or ultra-fine grain, in third stage separator, tell fines.
5. like the preparation method of the said modified coal ash of claim 3; It is characterized in that; It is in said second stage separator and third stage separator, to carry out that said spray surface chemical modification is handled, by being arranged at least one shower nozzle in said second stage separator and the third stage separator to said fine particle and fines surperficial direct spraying modified dose.
6. the preparation method of superfined flyash according to claim 1; It is characterized in that; Further comprise, will in said fine particle after said spraying chemical modification is handled and fines importing kneader, stir, kneading and heat treated, the strengthening surface coupling.
7. like the preparation method of the said superfined flyash of claim 6, it is characterized in that, at least one shower nozzle is set at said kneader top.
8. like the preparation method of the said modified coal ash of claim 5, it is characterized in that said properties-correcting agent is the vaporific dispersion liquid of coupling agent; Wherein, said coupling agent is any one or two or more mixing of silane, aluminic acid ester, titanic acid ester, zirconate; Its consumption is the 0.2-3% of said flyash weight; Said dispersion liquid is any one or two or more mixing of solvent oil, alcohol, ETHYLE ACETATE, trolamine, epoxy soybean oil, allyloxy propylene oxide, glycidyl ether; Its consumption is the 0.5-5% of said flyash weight.
9. the preparation method of modified coal ash according to claim 1 is characterized in that, further comprises, in the separator of the said second stage, the further sorting of fine particle more than said 800 orders is obtained ultra-fine grain; The particle diameter of said ultra-fine grain is 1200 orders or 2000 orders.
10. the modified coal ash for preparing of method according to claim 1 is characterized in that, one or more organic groups saturated or unsaturated structure of the particle surface chemically bonded of said modified coal ash, and activation index is greater than 0.9.
11. coal ash sorting and reforming apparatus is characterized in that under airtight negative pressure state, said device is used in the sorting fly ash grain, this particle surface being carried out modification, comprising:
Size separation equipment is used for the said flyash of sorting; It comprises first step separator and the second stage separator and the third stage separator that are communicated with successively with said first step separator;
Distributed and arranged is at said second stage separator and third stage separator top and/or at least one shower nozzle all around, and it is used for surperficial directly spraying modified dose to the fly ash grain of sorting;
And the kneader or the impeller that are tightly connected with said second stage separator and third stage separator respectively, be used to strengthen the Chemical bond of coupling agent and particle surface and the effect of coupled action.
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| CN103613299A (en) * | 2013-11-26 | 2014-03-05 | 柳州市圣诺科技有限公司 | Preparation method of fly ash |
| CN104119564A (en) * | 2014-07-02 | 2014-10-29 | 合肥和安机械制造有限公司 | Modified fly ash for heat shrinkable tube material and preparation method thereof |
| CN104212002A (en) * | 2014-08-21 | 2014-12-17 | 安徽吉安特种线缆制造有限公司 | Modified fly ash for low-temperature-resistant butyronitrile rubber cable material and preparation method of modified fly ash |
| CN105110672A (en) * | 2015-07-31 | 2015-12-02 | 武汉理工大学 | Method for homogeneously modifying pulverized coal ash by vapor deposition process |
| CN105419406A (en) * | 2015-12-19 | 2016-03-23 | 华南理工大学 | Modification method for improving whiteness of coal ash |
| CN106349531A (en) * | 2016-01-06 | 2017-01-25 | 临泉县泉河纳米植物新材料有限公司 | Filling reinforcing agent of rubber, and preparation method of filling reinforcing agent |
| CN106633251A (en) * | 2016-09-30 | 2017-05-10 | 浙江天达环保股份有限公司 | Butadiene styrene rubber filled with superfine coal ash and preparation method |
| CN108102176A (en) * | 2018-01-24 | 2018-06-01 | 合肥尚强电气科技有限公司 | Flame-retardant high-temperature-resistant insulating material for cable and preparation method thereof |
| CN108610659A (en) * | 2018-04-17 | 2018-10-02 | 郝亚明 | Aluminium hydroxide micro powder wet-process modified technique and its device |
| CN109134932A (en) * | 2018-08-29 | 2019-01-04 | 荣广磊 | Rubber product reinforcement modified coal ash and preparation method thereof |
| CN109517218A (en) * | 2018-10-24 | 2019-03-26 | 华东师范大学 | A kind of modified dust collection powder and its preparation method and application |
| CN109678376A (en) * | 2018-12-28 | 2019-04-26 | 武汉理工大学 | It is a kind of with diminishing, the flyash of viscosity reduction function and preparation method thereof |
| CN110818953A (en) * | 2019-11-18 | 2020-02-21 | 福州大学 | Preparation method and application of modified fly ash floating bead loaded DOPO |
| CN112500006A (en) * | 2020-12-04 | 2021-03-16 | 苏州娄城新材料科技有限公司 | Fly ash production method |
| CN113174149A (en) * | 2021-04-27 | 2021-07-27 | 山西奇色环保科技股份有限公司 | Method for preparing composite pigment filler for paint by using fly ash |
| CN115846350A (en) * | 2022-11-04 | 2023-03-28 | 上海理工大学 | Method for modifying biomass ash in grading manner |
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|---|---|---|---|---|
| CN103059457A (en) * | 2012-12-12 | 2013-04-24 | 安徽海纳川塑业科技有限公司 | Polyvinyl chloride tube containing modified coal ash and preparing method thereof |
| CN103059457B (en) * | 2012-12-12 | 2016-04-06 | 安徽海纳川塑业科技有限公司 | A kind of pvc tubing containing modified coal ash and preparation method thereof |
| CN103613299A (en) * | 2013-11-26 | 2014-03-05 | 柳州市圣诺科技有限公司 | Preparation method of fly ash |
| CN104119564A (en) * | 2014-07-02 | 2014-10-29 | 合肥和安机械制造有限公司 | Modified fly ash for heat shrinkable tube material and preparation method thereof |
| CN104212002A (en) * | 2014-08-21 | 2014-12-17 | 安徽吉安特种线缆制造有限公司 | Modified fly ash for low-temperature-resistant butyronitrile rubber cable material and preparation method of modified fly ash |
| CN105110672A (en) * | 2015-07-31 | 2015-12-02 | 武汉理工大学 | Method for homogeneously modifying pulverized coal ash by vapor deposition process |
| CN105419406A (en) * | 2015-12-19 | 2016-03-23 | 华南理工大学 | Modification method for improving whiteness of coal ash |
| CN106349531A (en) * | 2016-01-06 | 2017-01-25 | 临泉县泉河纳米植物新材料有限公司 | Filling reinforcing agent of rubber, and preparation method of filling reinforcing agent |
| CN106633251B (en) * | 2016-09-30 | 2018-09-07 | 浙江天地环保科技有限公司 | A kind of butadiene-styrene rubber and preparation method thereof of superfined flyash filling |
| CN106633251A (en) * | 2016-09-30 | 2017-05-10 | 浙江天达环保股份有限公司 | Butadiene styrene rubber filled with superfine coal ash and preparation method |
| CN108102176A (en) * | 2018-01-24 | 2018-06-01 | 合肥尚强电气科技有限公司 | Flame-retardant high-temperature-resistant insulating material for cable and preparation method thereof |
| CN108610659A (en) * | 2018-04-17 | 2018-10-02 | 郝亚明 | Aluminium hydroxide micro powder wet-process modified technique and its device |
| CN109134932A (en) * | 2018-08-29 | 2019-01-04 | 荣广磊 | Rubber product reinforcement modified coal ash and preparation method thereof |
| CN109517218A (en) * | 2018-10-24 | 2019-03-26 | 华东师范大学 | A kind of modified dust collection powder and its preparation method and application |
| CN109678376A (en) * | 2018-12-28 | 2019-04-26 | 武汉理工大学 | It is a kind of with diminishing, the flyash of viscosity reduction function and preparation method thereof |
| CN109678376B (en) * | 2018-12-28 | 2021-08-10 | 武汉理工大学 | Fly ash with water reducing and viscosity reducing functions and preparation method thereof |
| CN110818953A (en) * | 2019-11-18 | 2020-02-21 | 福州大学 | Preparation method and application of modified fly ash floating bead loaded DOPO |
| CN112500006A (en) * | 2020-12-04 | 2021-03-16 | 苏州娄城新材料科技有限公司 | Fly ash production method |
| CN113174149A (en) * | 2021-04-27 | 2021-07-27 | 山西奇色环保科技股份有限公司 | Method for preparing composite pigment filler for paint by using fly ash |
| CN115846350A (en) * | 2022-11-04 | 2023-03-28 | 上海理工大学 | Method for modifying biomass ash in grading manner |
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