CN104004241B - A kind of preparation method of coal-based functional enhancing powder body material - Google Patents
A kind of preparation method of coal-based functional enhancing powder body material Download PDFInfo
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Abstract
The preparation method of a kind of coal-based functional enhancing powder body material of the present invention, comprises the steps: 1) pulverized anthracite is broken into hard coal particle, be immersed in acid; 2) the hard coal particle after acid soak is joined in swelling agent carry out swelling treatment; 3) the hard coal particle after swelling treatment is joined in the Glacial acetic acid of concentration 20wt% ~ 30wt% carry out intercalation modifying; Again the hard coal particle after Glacial acetic acid intercalation modifying is joined in acrylamide and carry out intercalation modifying; 4) by step 3) the hard coal particle that obtains mixes with properties-correcting agent, in ball mill, carry out ball milling; 5) by step 4) obtain the drying of hard coal particle dehydration, obtained product.The present invention adopts hard coal, through acidleach process; Then carry out swelling and intercalation modifying, make the reaction force attenuation between its fragrant slice Rotating fields; Then use mechanical-chemical modification, make anthracitic granularity refinement, surfactivity improves, and reinforcing property is remarkable, can improve the over-all properties of rubber composite.
Description
Technical field
The present invention relates to functional powder Material Field, especially relate to a kind of preparation method of coal-based functional enhancing powder body material.
Background technology
Coal forms [HaenelMW.Recentprogressincoalstructure [J] .Fuel, 1992,71 (11): 1211-1223.] primarily of condensation aromatic nucleus elementary cell and a small amount of hydroaromatic ring, alicyclic ring and heterocycle etc.Coal texture unit periphery [1. ShinnJH.Fromcoaltosingle-stageandtwo-stageproducts:Areac tivemodelofcoalstructure [J] .Fuel except being connected to alkyl group side chain, 1984, 63 (9): 1187-1196. 2. LiuD, QiuJ, LiJ.Physicalstructureandcombustionpropertiesofsuperfinep ulverizedcoalparticle [J] .Fuel, 2002, 81 (6): 793-797.], also have some as carboxyl (-COOH), hydroxyl (-OH), the oxygen-containing functional group such as methoxyl group and ehter bond and a small amount of mercaptan (R-SH), thioether, disulfide, nitrogenous and the sulfur-bearing functional group such as heterocycle sulphur, impart the activity that coal is higher, be conducive to the chemical modification of coal.Therefore, take coal as research [the 1. LiuD that the coal-based functional supporting material of starting material development research improves the physical and mechanical properties of polymer materials, QiuJ, LiJ.Physicalstructureandcombustionpropertiesofsuperfinep ulverizedcoalparticle [J] .Fuel, 2002, 81 (6): 793-797. 2. Wu Chen. the industrialized preparing process of modification coal measures low density filler and application [J]. Coal Chemical Industry, 2006, 123 (2): 38-39.], cause the close attention [Li Kanshe of domestic and international research worker, Zhou Anning. coal-based Materials [J]. polymer material science and engineering, 2001, 17 (4): 19-21.].
In the thirties in 20th century, levigate brown coal powder mixes with benzene by the F.Fischer of Germany, is mixingly pressed into sheet material, and this is the preparation method the earliest of coal-based matrix material.Early sixties, Japan and Germany, in order to make up the under-supply of carbon black, have been carried out and have been replaced carbon black as the research of loading material of rubber using superfine pulverized coal, afterwards because starting material are not enough and technology, are forced to stop research.After the eighties, Germany has carried out studying to superfine pulverized coal again, is pulverized by coal dust through dry type, prepares filler styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, paracril, ethylene-propylene rubber(EPR) and viton to certain strengthening action, and its processing characteristics is better.The eighties, Beijing Coal chemistry institute and rubber studying and designing institute, Beijing combine to make further research the application of coal dust in rubber and achieve initial achievements.By exploration for many years, the technique of coal rubber composite and technology have had larger improvement, but be modified as master mainly with superfine grinding, the consistency of powder and reinforcing larger with carbon black gap, urgent need improves further [1. Wu Chen. the industrialized preparing process of modification coal measures low density filler and application [J]. Coal Chemical Industry, 2006,123 (2): 38-39., 2. Lu Jianjun, Xie Kechang. coal-based polymer composites present Research and development trend [J]. chemical industry is in progress, 2001,22 (12): 1265-1268.].Existing technique means and technique, and the application in the polymeric material of the real alternative carbon black of unrealized coal-based filler are larger from industrial applications gap.
Coal organic macromolecule is formed by the different aromatic hydrocarbon of condensation level and alicyclic ring, heterocycle structure unit combination, and its structure presents change [HirschPB.X-RayScatteringfromCoals [J] .ProceedingsoftheRoyalSocietyofLondon.SeriesA of certain regularity along with the increase of carbon content, MathematicalandPhysicalSciences, 1954,226:143-169.].Along with the increase of degree of coalification, aromatic nucleus condensation level increases gradually, bridged bond, side chain and functional group reduce gradually, to the hard coal stage, the more ordering of coal molecular arrangement, fragrant lamella degree of orientation increases, form the laminate structure [Ren Yaojian of similar graphite crystal, Sun Zhi. the progress [J] of polymkeric substance/coal matrix material. engineering plastics are applied, and 2009,37 (1): 84-87.].But the agent structure periphery of the fragrant lamella of coal is also connected to some alkyl chains, oxygen-containing functional group and nitrogenous and sulfur-bearing functional group on a small quantity, structural nexus is tight between layers, particle size is larger, current grinding and processing modification technology, be difficult to limellar stripping and refinement, cause its modified powder material strengthening action to polymkeric substance not obvious.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of coal-based functional enhancing powder body material.The method is in the deficiency of existing superfine grinding modification technology in the coal-based filler process of preparation alternative carbon black, and carbon black manufacturing process is complicated, and environmental pollution is serious, on expensive basis; High degree of coalification hard coal is utilized to have the laminate structure feature of seemingly graphite, the novel process of acidleach-swelling-intercalation-mechanical-chemical modification is adopted anthracitic laminated structure to be dissociated, a kind of coal-based functional enhancing powder body material with high structure-activity and consistency has been prepared by spraying dry, alternative carbon black, significantly improve the physical and mechanical properties of rubber composite, improve and anthraciticly utilize added value.
For solving above-mentioned first technical problem, the preparation method of a kind of coal-based functional enhancing powder body material of the present invention, comprises the steps:
1) pulverized anthracite is broken into hard coal particle, is immersed in acid;
2) the hard coal particle after acid soak is joined in swelling agent carry out swelling treatment;
3) the hard coal particle after swelling treatment is joined in the Glacial acetic acid of concentration 20wt% ~ 30wt% carry out intercalation modifying; Again the hard coal particle after Glacial acetic acid intercalation modifying is joined in acrylamide and carry out intercalation modifying;
4) by step 3) the hard coal particle that obtains mixes with properties-correcting agent, in ball mill, carry out ball milling, and complete wet method mechanical force and chemical and to delaminate modification;
5) by step 4) obtain the drying of hard coal particle dehydration, obtained product.
Preferably, step 1) in, particle diameter≤20 micron of described hard coal particle.
Preferably, step 1) in, described acid is sulfuric acid, hydrochloric acid, nitric acid or hydrofluoric acid.
Preferably, step 1) in, described hard coal particle is 1: 1 ~ 1: 4 with the mass ratio of acid.
Preferably, step 1) in, described hard coal particle be immersed in acid time >=6 hours; Temperature >=60 DEG C.
Preferably, step 2) in, described swelling agent be selected from following material one or more: toluene, dimethylbenzene, aniline, tetrahydrofuran (THF), methane amide, N-N dimethyl formamide.
Preferably, step 2) in, the mass ratio of described hard coal particle and swelling agent is 1: 1.5 ~ 2.5.
Preferably, step 2) in, the temperature of swelling treatment is 78 ~ 82 DEG C.
Preferably, step 3) in, the condition of intercalation modifying is: stirring reaction >=24h under the constant temperature of 88 ~ 92 DEG C in stripping reaction still.
Preferably, step 4) in, described properties-correcting agent is lipid acid, epoxy radicals silicone hydride, vinyl silanes, aminosilane or hydrosulphonyl silane.
Preferably, step 4) in, the mass ratio of described hard coal particle and properties-correcting agent is 1: 0.01 ~ 0.03.
Preferably, step 4) in, described ball mill is shape planetary ball mill, and ball milling condition is: rotating speed >=550 rev/min; Ball proportioning is 3: 1, and ratio of grinding media to material is 6: 1, time >=6 hours.
Preferably, step 5) in, described in dehydrate employing Highspeedcentrifugingandsprayingdrier.
Beneficial effect of the present invention is as follows:
The present invention adopts the hard coal had like graphite laminate structure, removes the ash content be wherein mingled with through acidleach process; Then carry out swelling and intercalation modifying, make the reaction force attenuation between its fragrant slice Rotating fields, volumetric expansion; Then adopt mechanical force and chemical to delaminate modification, fragrant lamella dissociates, and makes the refinement greatly of anthracitic granularity, and surfactivity improves, and reinforcing property is remarkable, significantly can improve the over-all properties of rubber composite, improves added value.The raw material sources of this preparation technology is extensive, and environmental contamination is little, is easy to mass production.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail
Fig. 1 is the multi-layer sheet structure SEM photo of the swelling coal of pyridine/dimethylbenzene;
Fig. 2 is the SEM photo of coal-based functional enhancing powder body material prepared by example 4.
Embodiment
Embodiment 1
To be hard coal and the concentration of 10um by granularity be 60% sulfuric acid in mass ratio 1: 3 ratio mix, under the condition of constant temperature 60 DEG C, soak reaction 72h, through deionized water wash solution to neutral, remove the impure mineral in coal, obtain the coal sample of purifying.The mixing solutions of the acidleach coal sample after purifying and dimethylbenzene/methane amide in mass ratio 1: 2 ratio mix, swelling treatment reaction 24h under the constant temperature of 80 DEG C, then uses whizzer under the condition of 5000 turns/min by coal sample centrifugation out.Then, first add the glacial acetic acid aqueous solution of mass concentration 20% in the coal sample that swelling treatment is crossed, the mass ratio of coal and Glacial acetic acid is 1: 2, stirring reaction 24h under the constant temperature of 90 DEG C in stripping reaction still; Then add the acrylamide doubling ature of coal amount, in glass reaction still, react 24h again with same condition.Finally, by the coal sample centrifugation after intercalation, add the deionized water of homogenous quantities, and the epoxy radicals silicone hydride properties-correcting agent of 1.5% times of ature of coal amount, delaminate modification 6h under the condition of 550r/min, ball proportioning 3: 1, ratio of grinding media to material 6: 1 in shape planetary ball mill.Final spraying dry, the coal based activated powder that acquisition d90 is 2.1um, loose bulk density is 0.11g/cm3.
Adopt the method for melt blending, according to national standard inspection formula, coal based activated powder and styrene-butadiene rubber(SBR) are carried out melt blending, obtained coal-based styrene-butadiene rubber composite material, its tensile strength reaches 16.77MPa, and 100% tensile modulus is 2.41MPa, 300% tensile modulus is 6.95MPa, shore hardness 55, tear strength 27.5KN/m, elongation at break 425%.
Embodiment 2
To be hard coal and the concentration of 20um by granularity be 40% hydrofluoric acid in mass ratio 1: 2 ratio mix, under the condition of constant temperature 60 DEG C, soak reaction 72h, through deionized water wash solution to neutral, remove the impure mineral in coal, obtain the coal sample of purifying.The mixing solutions of the acidleach coal sample after purifying and aniline/methane amide in mass ratio 1: 2 ratio mix, swelling treatment reaction 24h under the constant temperature of 80 DEG C, then uses whizzer under the condition of 5000 turns/min by coal sample centrifugation out.Then, first add the glacial acetic acid aqueous solution of mass concentration 20% in the coal sample that swelling treatment is crossed, the mass ratio of coal and Glacial acetic acid is 1: 2, stirring reaction 24h under the constant temperature of 90 DEG C in stripping reaction still; Then add the acrylamide doubling ature of coal amount, in glass reaction still, react 24h again with same condition.Finally, by the coal sample centrifugation after intercalation, add the deionized water of homogenous quantities, and amino silane modified dose of 2.0% times of ature of coal amount, delaminate modification 6h under the condition of 550r/min, ball proportioning 3: 1, ratio of grinding media to material 6: 1 in shape planetary ball mill.Final spraying dry, the coal based activated powder that acquisition d90 is-1.8um, loose bulk density is 0.09g/cm3.
Adopt the method for melt blending, according to national standard inspection formula, coal based activated powder and styrene-butadiene rubber(SBR) are carried out melt blending, obtained coal-based styrene-butadiene rubber composite material, its tensile strength reaches 17.91MPa, and 100% tensile modulus is 2.53MPa, 300% tensile modulus is 7.32MPa, shore hardness 58, tear strength 29.3KN/m, elongation at break 463%.
Embodiment 3
To be hard coal and the concentration of 15um by granularity be 40% hydrofluoric acid in mass ratio 1: 1 ratio mix, under the condition of constant temperature 60 DEG C, soak reaction 72h, through deionized water wash solution to neutral, remove the impure mineral in coal, obtain the coal sample of purifying.The mixing solutions of the acidleach coal sample after purifying and toluene/dimethylbenzene in mass ratio 1: 2 ratio mix, swelling treatment reaction 24h under the constant temperature of 80 DEG C, then uses whizzer under the condition of 5000 turns/min by coal sample centrifugation out.Then, first add the glacial acetic acid aqueous solution of mass concentration 30% in the coal sample that swelling treatment is crossed, the mass ratio of coal and Glacial acetic acid is 1: 2, stirring reaction 24h under the constant temperature of 90 DEG C in stripping reaction still; Then add the acrylamide doubling ature of coal amount, in glass reaction still, react 24h again with same condition.Finally, by the coal sample centrifugation after intercalation, add the deionized water of homogenous quantities, and the vinyl silanes properties-correcting agent of 2.0% times of ature of coal amount, delaminate modification 6h under the condition of 550r/min, ball proportioning 3: 1, ratio of grinding media to material 6: 1 in shape planetary ball mill.Final spraying dry, the coal based activated powder that acquisition d90 is-1.7um, loose bulk density is 0.085g/cm3.
Adopt the method for melt blending, according to national standard inspection formula, coal based activated powder and styrene-butadiene rubber(SBR) are carried out melt blending, obtained coal-based styrene-butadiene rubber composite material, its tensile strength reaches 18.28MPa, and 100% tensile modulus is 2.74MPa, 300% tensile modulus is 7.71MPa, shore hardness 59, tear strength 32.8KN/m, elongation at break 475%.
Embodiment 4
To be hard coal and the concentration of 5um by granularity be 40% hydrofluoric acid in mass ratio 1: 4 ratio mix, under the condition of constant temperature 60 DEG C, soak reaction 72h, through deionized water wash solution to neutral, remove the impure mineral in coal, obtain the coal sample of purifying.The mixing solutions of the acidleach coal sample after purifying and pyridine/dimethylbenzene in mass ratio 1: 2 ratio mix, swelling treatment reaction 24h under the constant temperature of 80 DEG C, then use whizzer under the condition of 5000 turns/min by coal sample centrifugation out, the interlayer structure change of swelling coal as shown in Figure 1.Then, first add the glacial acetic acid aqueous solution of mass concentration 30% in the coal sample that swelling treatment is crossed, the mass ratio of coal and Glacial acetic acid is 1: 2, stirring reaction 24h under the constant temperature of 90 DEG C in stripping reaction still; Then add the acrylamide doubling ature of coal amount, in glass reaction still, react 24h again with same condition.Finally, by the coal sample centrifugation after intercalation, add the deionized water of homogenous quantities, and the epoxy radicals silicone hydride of each 1.0% times of ature of coal amount and hydrosulphonyl silane properties-correcting agent, delaminate modification 6h under the condition of 550r/min, ball proportioning 3: 1, ratio of grinding media to material 6: 1 in shape planetary ball mill.Final spraying dry, the coal based activated powder that acquisition d90 is-1.4um, loose bulk density is 0.08g/cm3, particle is strip (Fig. 2).
Adopt the method for melt blending, according to national standard inspection formula, coal based activated powder and styrene-butadiene rubber(SBR) are carried out melt blending, obtained coal-based styrene-butadiene rubber composite material, its tensile strength reaches 20.57MPa, and 100% tensile modulus is 2.94MPa, 300% tensile modulus is 7.93MPa, shore hardness 61, tear strength 35.7KN/m, elongation at break 486%.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (13)
1. a preparation method for coal-based functional enhancing powder body material, is characterized in that, comprise the steps:
1) pulverized anthracite is broken into hard coal particle, is immersed in acid;
2) the hard coal particle after acid soak is joined in swelling agent carry out swelling treatment;
3) the hard coal particle after swelling treatment is joined in the Glacial acetic acid of concentration 20wt% ~ 30wt% carry out intercalation modifying; Again the hard coal particle after Glacial acetic acid intercalation modifying is joined in acrylamide and carry out intercalation modifying;
4) by step 3) the hard coal particle that obtains mixes with properties-correcting agent, in ball mill, carry out ball milling, and complete wet method mechanical force and chemical and to delaminate modification;
5) by step 4) obtain the drying of hard coal particle dehydration, obtained product.
2. preparation method according to claim 1, is characterized in that: step 1) in, particle diameter≤20 micron of described hard coal particle.
3. preparation method according to claim 1, is characterized in that: step 1) in, described acid is sulfuric acid, hydrochloric acid, nitric acid or hydrofluoric acid.
4. preparation method according to claim 1, is characterized in that: step 1) in, described hard coal particle is 1: 1 ~ 1: 4 with the mass ratio of acid.
5. preparation method according to claim 1, is characterized in that: step 1) in, described hard coal particle be immersed in acid time >=6 hours; Temperature >=60 DEG C.
6. preparation method according to claim 1, is characterized in that: step 2) in, described swelling agent be selected from following material one or more: toluene, dimethylbenzene, aniline, tetrahydrofuran (THF), methane amide, N-N dimethyl formamide.
7. preparation method according to claim 1, is characterized in that: step 2) in, the mass ratio of described hard coal particle and swelling agent is 1: 1.5 ~ 2.5.
8. preparation method according to claim 1, is characterized in that: step 2) in, the temperature of swelling treatment is 78 ~ 82 DEG C.
9. preparation method according to claim 1, is characterized in that: step 3) in, the condition of intercalation modifying is: stirring reaction >=24h under the constant temperature of 88 ~ 92 DEG C in stripping reaction still.
10. preparation method according to claim 1, is characterized in that: step 4) in, described properties-correcting agent is lipid acid, epoxy radicals silicone hydride, vinyl silanes, aminosilane or hydrosulphonyl silane.
11. preparation methods according to claim 1, is characterized in that: step 4) in, the mass ratio of described hard coal particle and properties-correcting agent is 1: 0.01 ~ 0.03.
12. preparation methods according to claim 1, is characterized in that: step 4) in, described ball mill is shape planetary ball mill, and ball milling condition is: rotating speed >=550 rev/min; Ball proportioning is 3: 1, and ratio of grinding media to material is 6: 1, time >=6 hours.
13. preparation methods according to claim 1, is characterized in that: step 5) in, described in dehydrate employing Highspeedcentrifugingandsprayingdrier.
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| CN116443850A (en) * | 2023-05-04 | 2023-07-18 | 赣州立探新能源科技有限公司 | Nitrogen-doped coal-based hard carbon material, preparation method and application thereof, and secondary battery |
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| CN101746768A (en) * | 2009-12-29 | 2010-06-23 | 中国矿业大学(北京) | Coal-series hard kaolinite stripping method capable of keeping crystal form of kaolinite |
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| CN101746768A (en) * | 2009-12-29 | 2010-06-23 | 中国矿业大学(北京) | Coal-series hard kaolinite stripping method capable of keeping crystal form of kaolinite |
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| 煤基功能性填料的研究进展;张玉德 等;《化工新型材料》;20130731;第41卷(第7期);第3-5页 * |
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