CN102530933B - Artificial graphite product taking emulsified asphalt as binder and preparation method thereof - Google Patents
Artificial graphite product taking emulsified asphalt as binder and preparation method thereof Download PDFInfo
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- CN102530933B CN102530933B CN201110456649.0A CN201110456649A CN102530933B CN 102530933 B CN102530933 B CN 102530933B CN 201110456649 A CN201110456649 A CN 201110456649A CN 102530933 B CN102530933 B CN 102530933B
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- 239000011230 binding agent Substances 0.000 title claims abstract description 97
- 239000010426 asphalt Substances 0.000 title claims abstract description 81
- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 103
- 239000010439 graphite Substances 0.000 claims abstract description 103
- 238000005087 graphitization Methods 0.000 claims abstract description 22
- 238000007598 dipping method Methods 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000006253 pitch coke Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000571 coke Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000011295 pitch Substances 0.000 claims description 65
- 239000013081 microcrystal Substances 0.000 claims description 46
- 239000002931 mesocarbon microbead Substances 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 238000005056 compaction Methods 0.000 claims description 7
- 238000000462 isostatic pressing Methods 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000011294 coal tar pitch Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001311 chemical methods and process Methods 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 238000000053 physical method Methods 0.000 claims description 4
- -1 secondary Jiao Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000011339 hard pitch Substances 0.000 claims description 3
- VYQRBKCKQCRYEE-UHFFFAOYSA-N ctk1a7239 Chemical compound C12=CC=CC=C2N2CC=CC3=NC=CC1=C32 VYQRBKCKQCRYEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011301 petroleum pitch Substances 0.000 claims description 2
- 239000011338 soft pitch Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 239000011325 microbead Substances 0.000 abstract 2
- 239000002006 petroleum coke Substances 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000004898 kneading Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000006424 Flood reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011305 binder pitch Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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Abstract
The invention discloses an artificial graphite product taking emulsified asphalt as a binder and a preparation method thereof. The practical mass ratio of the binder and aggregate in the artificial graphite product is (0.05-0.70):1; the aggregate is one or more of petroleum coke, pitch coke, secondary coke, natural amorphous graphite, intermediate-phase carbon microbead or graphite return scrap; different aggregates do not have a limited proportion; when the main body of the aggregate is the natural amorphous graphite, the natural amorphous graphite accounts for 50-100wt% of the aggregate, the residual material is one or more of petroleum coke, pitch coke, secondary coke, intermediate-phase carbon microbead or graphite return scrap, and all materials do not have the limited proportion; and the binder is the emulsified asphalt. The preparation method comprises the following steps: firstly, evenly mixing the emulsified asphalt with the aggregate to obtain powder; forming, roasting, dipping and secondarily roasting the powder; and finally, carrying out graphitization processing. After meeting each other, the emulsified asphalt and the aggregate are randomly cracked to guarantee the coating evenness of the aggregate by the asphalt. The emulsified asphalt is completely in a water system, the organic solvent does not need to be used, and the operation process is environmentally-friendly, simple and convenient.
Description
Technical field
The invention belongs to graphite product technical field, be specifically related to a kind of synthetic graphite goods of making binding agent with emulsified bitumen and preparation method thereof.
Background technology
Isotropic graphite is the synthetic graphite material of a class top grade, in many high-technology field extensive application.Generally, use the isotropic nature of describing graphite along the ratio of the thermal linear expansion coefficient in two orthogonal directions, be called isotropy degree.Regulation according to ASTM standard C 709-06 to nuclear graphite, isotropy degree is between the isotropic graphite that belongs to of 1.00-1.10; Between the title nearly isotropy graphite of 1.10-1.15; Be greater than 1.15 be called anisotropy graphite.
The Production Flow Chart of isotropic graphite and common graphite goods are basic identical.In the production of isotropic graphite, binding agent and very important with the kneading process of aggregate.Particle and powdery aggregate do not have formability, need to rely on binding agent just can be formed with the raw product of definite shape and intensity.Binding agent is also transformed into the carbonaceous the same with aggregate in follow-up carbonization process, and particles of aggregates is bonded together.The bonding state of binding agent and aggregate affects the final performance of graphite to a great extent.Current most popular binding agent is coal-tar pitch, and the feature that the binder pitch of excellent performance should have has: 1. higher softening temperature.When pitch softening point is higher, carbonization yield is also high, produces favourable to graphite.The softening temperature of modified pitch is generally greater than 100 DEG C, and coking rate is greater than 50%, and performance is better than common mid-temperature pitch.2. there is good affinity with aggregate.The affinity of binder pitch and aggregate is good, aggregate surface fully can be infiltrated, and the compound forming when kneading is even.Except pitch, also useful thermoplastic resin makees binding agent, as resol, furane resin etc.
Softening temperature is one of important physical properties of coal-tar pitch.75 DEG C of following title viscid bitumens of general softening temperature; The title mid-temperature pitch of 75-90 DEG C; More than 90 DEG C is hard pitch.Modified pitch be by mid-temperature pitch through aggregation processing, softening temperature is generally higher than 100 DEG C, quinoline insolubles content approximately 10%, carbonization yield is higher.The external generally binding agent for the production of carbon product with the alternative mid-temperature pitch of modified pitch at present.
Coal-tar pitch is the macromolecular mixed systems of a series of condensed ring.Organizing asphaltogenic compound may have hundreds of, thousands of kinds more than, complicated component, thereby also different to the effect of different solvents.Pitch can not be dissolved in certain single solvent completely, but can extract successively with several different solvents, and pitch is divided into different components studied.Conventional solvent is as toluene, hexane, tetrahydrofuran (THF), pyridine, quinoline etc.As pitch being divided into toluene extraction, toluene is solvable, toluene insolubles.Toluene insolubles continues can be divided into quinoline solvend, quinoline insolubles with quinoline extraction.Wherein toluene insolubles-quinoline solvend claims β resin, and concerning carbon material, the pitch charcoal yield that β resin content is high is generally also high.
Binding agent mixes with aggregate mutually by kneading, and the object that kneading will reach is: 1. make different gradation aggregate fully mix.2. make binding agent and aggregate well infiltrate, wrap up equably a layer binder at aggregate surface.3. make part binding agent penetrate in the hole of aggregate.What application was maximum at present is Double shaft stirring kneading machine.When operation, aggregate and binding agent add from upper end, heated and stirred.Kneading temperature is determined according to the temperature-viscosity curve of coal-tar pitch, is generally selected in the violent temperature range declining of asphalt viscosity, conventionally than the high 50-70 DEG C of pitch softening point.
But in the time preparing fine graphite, hyperfine structure graphite and isotropic graphite, aggregate size is tiny, traditional kneading method there will be problem.Fine granularity surface area of aggregate is larger, and pitch usage quantity increases, and causes certain difficulty to roasting.And after roasting, the density of goods becomes lower, may increase dipping number of times.On the other hand, aggregate size is more carefully more not easy to mix with pitch, causes in goods and contains defectiveness, and the uneven first-class problem of weave construction, adopts the prolongation kneading time to be tackled at present conventionally.
Summary of the invention
The shortcoming existing in order to overcome above-mentioned prior art, the object of the present invention is to provide a kind of synthetic graphite goods of making binding agent with emulsified bitumen and preparation method thereof, taking emulsified bitumen as binding agent, after emulsified bitumen and aggregate meet, emulsified bitumen divides at random, ensure the homogeneity that pitch is coated to aggregate, therefore to some molding mode, as mold pressing, etc. static pressure, the comparable general kneading mode of consumption of binder is few, emulsified bitumen is complete water system, without with an organic solvent, therefore operating process environmental protection is easy.
For achieving the above object, the present invention by the following technical solutions:
A kind of synthetic graphite goods of making binding agent with emulsified bitumen, its raw material comprises binding agent and aggregate, the mass ratio of binding agent and aggregate is (0.05-0.70): 1, and described aggregate is: one or more in refinery coke, pitch coke, secondary Jiao, natural micro crystal graphite, MCMB or graphite returns; In the time that aggregate is two or more, different aggregates do not have limited proportion each other; In the time that the main body of aggregate is natural micro crystal graphite, natural micro crystal graphite accounts for the 50-100% of aggregate quality, and its clout is one or more in pitch coke, refinery coke, secondary Jiao, MCMB or graphite returns, and there is no each other limited proportion; Described binding agent is emulsified bitumen, pitch solid phase weight content 40-70%, pitch softening point 60-100 DEG C.
Isotropy degree α≤1.15 of described synthetic graphite goods, are specially: distinguish the goods of compression molding, extrusion molding, isotropy degree α≤1.15 by forming method; Vibratory compaction and isostatic pressing goods, α≤1.10; Distinguish secondary Jiao, natural micro crystal graphite, MCMB resulting product, α≤1.10 by aggregate type; Add refinery coke, pitch coke and other aggregate resulting product α≤1.15.
Prepare a method of making the synthetic graphite goods of binding agent with emulsified bitumen, using emulsified bitumen as binding agent, comprise the following steps:
The first step, be (0.05-0.70) by mass ratio: 1 emulsified bitumen mixes with aggregate: the actual mass of binding agent calculates according to the solid phase weight content of emulsified bitumen, emulsified bitumen as required can thin up be 1～10 times of emulsified bitumen weight, be adjusted to required viscosity, then emulsified bitumen and aggregate are placed in to stirrer, mix, after having divided, filter unnecessary liquid, dry at 50-150 DEG C, moisture content is evaporated completely, and the product that is uniformly mixed, is ground into the powder of granularity≤5mm;
Described emulsified bitumen, pitch weight content 40-70%, pitch softening point 60-100 DEG C;
Described aggregate is one or more in refinery coke, pitch coke, secondary Jiao, natural micro crystal graphite, MCMB or graphite returns, in the time that the main body of aggregate is natural micro crystal graphite, natural micro crystal graphite accounts for the 50-100% of aggregate quality, its clout is one or more in pitch coke, refinery coke, secondary Jiao, MCMB or graphite returns, and there is no each other limited proportion;
Second step, adopts compression molding, extrusion molding, vibratory compaction or isostatic pressing to produce moulding graphite green compact to the even mixed powder of gained aggregate and binding agent;
The 3rd step, carries out roasting to moulding graphite green compact, maturing temperature 800-1200 DEG C, roasting time 10-900 hour;
The 4th step, baked moulding graphite green compact are carried out to dipping and the re-baking of 1-3 time, when dipping, first moulding graphite green compact are carried out to 200 DEG C of preheatings, time 3-5 hour, then impregnating autoclave is vacuumized, pressure≤0.02MPa, adds the pitch of melting, under 0.3-1.5MPa pressure, flood, impregnated goods are at 800-1000 DEG C of re-baking, roasting time 10-100 hour, and the re-baking temperature of each time is identical or different;
The 5th step, the goods that complete dipping and re-baking are carried out to graphitization processing, graphitization processing temperature is 2200-3000 DEG C, 10 days to 20 days used time, if aggregate main body is natural graphite or graphite returns and fixed carbon content >=98%, natural graphite or graphite returns are in aggregate when shared mass ratio >=50%, in the time requiring the folding strength of isotropic graphite product to be greater than 50MPa, can not carry out graphitization processing, last re-baking temperature is 900-1200 DEG C.
Emulsified bitumen described in the first step is soft pitch, mid-temperature pitch, hard pitch or modified pitch, coal-tar pitch or petroleum pitch.
Emulsified bitumen carbonization yield described in the first step is 15-50%, and grain diameter is 1-3 μ m.
Natural micro crystal graphite described in the first step is purified natural micro crystal graphite, raw ore after chemistry or physical method are purified, the natural micro crystal graphite that fixed carbon content is 90-99.99%, its granularity is 1-150 μ m.
Compared to the prior art, tool has the following advantages in the present invention:
1, emulsified bitumen, be by pitch under the effect of emulsifying agent, by mechanical shearing effect, the dispersion system of the bitumen particle of formation in water, the softening temperature 60-110 DEG C of pitch used, carbonization yield 15-50%, after meeting with aggregate, emulsified bitumen divides immediately, has ensured the homogeneity that pitch is coated to aggregate, therefore to some molding mode, as mold pressing, etc. static pressure, the comparable general kneading mode of consumption of binder is few.
2, emulsified bitumen is complete water system, without with an organic solvent, therefore operating process environmental protection is easy.
3, emulsified bitumen is used in a large number aspect capital construction, can be mass-produced, and cost is lower.The emulsified bitumen grain diameter 1-3 μ m forming, has good stability in storage.
Embodiment
By embodiment, the present invention is described in more detail below.
Embodiment mono-
A kind of synthetic graphite goods of making binding agent with emulsified bitumen of the present embodiment, its raw material comprises emulsified bitumen binding agent and aggregate, the mass ratio of actual binding agent and aggregate is 0.3: 1, the component of described aggregate is natural micro crystal graphite, described natural micro crystal graphite is purified natural micro crystal graphite, fixed carbon content is 99.9%, granularity≤40 μ m.Described binding agent is emulsified bitumen, 60 DEG C of pitch softening points.Actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen.
A kind of preparation method who makes the synthetic graphite goods of binding agent with emulsified bitumen of the present embodiment, comprises the following steps:
The first step, the binding agent that is 0.3: 1 by actual mass ratio and aggregate are in room temperature directly in stirrer for mixing, and the component of described aggregate is: natural micro crystal graphite accounts for 100% of aggregate quality; Described micro crystal graphite is purified natural micro crystal graphite, and fixed carbon content is 99.9%, granularity≤40 μ m.Described binding agent is emulsified bitumen, pitch softening point is 60 DEG C, described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen, after having divided, filter unnecessary liquid, dry at 50 DEG C, moisture content is evaporated completely, the product that is uniformly mixed, is ground into the powder of granularity≤5mm;
Second step, adopts vibratory compaction to produce Φ 50mm moulding graphite green compact to the even mixed powder of gained aggregate and binding agent;
The 3rd step, carries out roasting to moulding graphite green compact, and maturing temperature is 1000 DEG C, roasting time 10 hours;
The 4th step, carries out 2 times to baked moulding graphite green compact and floods and re-baking.When dipping, first preheating 3 hours at 200 DEG C, then impregnating autoclave is vacuumized to reach≤0.02MPa, pours into the pitch of melting, under 1.2MPa pressure, floods, and impregnated goods are at 800 DEG C of re-bakings, roasting time 10 hours;
The 5th step, carries out graphitization processing to the goods that complete dipping and re-baking, and graphitization processing temperature is 2800 DEG C, 14 days used times.
Gained graphite product: volume density 1.85g/cm
3, degree of graphitization 91%, isotropy degree α=1.04, folding strength 26MPa.
Embodiment bis-
A kind of synthetic graphite goods of making binding agent with emulsified bitumen of the present embodiment, its raw material comprises binding agent and aggregate, the mass ratio of actual binding agent and aggregate is 0.3: 1, and the component of described aggregate is: natural micro crystal graphite accounts for 90% of aggregate quality, and MCMB accounts for 10%; Described micro crystal graphite is purified natural micro crystal graphite, and fixed carbon content is 99.9%, granularity≤40 μ m, and described MCMB is through slight preoxidation, granularity≤20 μ m.Described binding agent is emulsified bitumen, 60 DEG C of pitch softening points, and described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen.
A kind of preparation method who makes the synthetic graphite goods of binding agent with emulsified bitumen of the present embodiment, comprises the following steps:
The first step, the binding agent that is 0.3: 1 by actual mass ratio and aggregate are at room temperature, even in stirrer for mixing, and the component of described aggregate is: natural micro crystal graphite accounts for 90% of aggregate quality, and MCMB accounts for 10%; Described natural micro crystal graphite is purified natural micro crystal graphite, and fixed carbon content is 99.9%, granularity≤40 μ m.Described MCMB is through slight preoxidation, granularity≤20 μ m.Described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen, after having divided, filters unnecessary liquid, dry at 80 DEG C, and moisture content is evaporated completely, and the product that is uniformly mixed is ground into the powder of granularity≤3mm;
Second step, adopts compression molding to produce moulding graphite green compact to the even mixed powder of gained aggregate and binding agent, mould Φ 300 × 300 (mm), and pressuring method is Bidirectional-pressure, pressure 60MPa;
The 3rd step, carries out roasting to moulding graphite green compact, and maturing temperature is 1200 DEG C, roasting time 900 hours;
The 4th step, carries out 3 times to baked goods and floods and re-baking, when dipping, first preheating 4 hours at 200 DEG C, then impregnating autoclave is vacuumized to reach≤0.02MPa, pour into the pitch of melting, under 1.0MPa pressure, flood the impregnated goods of first pass re-baking at 900 DEG C.The temperature of second time impregnated goods re-baking is 1200 DEG C, roasting time 100 hours;
The 5th step, carries out graphitization processing to the goods that complete dipping and re-baking, and graphitization processing temperature is 2700 DEG C, 15 days used times.
Gained graphite product: volume density 1.89g/cm
3, degree of graphitization 87%, anisotropic index α=1.09, folding strength 31MPa.
Embodiment tri-
A kind of synthetic graphite goods of making binding agent with emulsified bitumen of the present embodiment, its raw material comprises binding agent and aggregate, the mass ratio of actual binding agent and aggregate is 0.7: 1, and the component of described aggregate is: natural micro crystal graphite accounts for 50% of aggregate quality, and MCMB accounts for 50%; Described micro crystal graphite is purified natural micro crystal graphite, and fixed carbon content is 99.9%, granularity≤40 μ m.Described MCMB is through slight preoxidation, granularity≤20 μ m.Described binding agent is emulsified bitumen, 70 DEG C of pitch softening points, and described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen.
A kind of preparation method who makes the synthetic graphite goods of binding agent with emulsified bitumen of the present embodiment, comprises the following steps:
The first step, the binding agent that is 0.7: 1 by actual mass ratio and aggregate at room temperature, evenly mix in stirrer, and the component of described aggregate is: natural micro crystal graphite accounts for 50% of aggregate quality, and MCMB accounts for 50%; Described natural micro crystal graphite is purified natural micro crystal graphite, raw ore after chemistry or physical method are purified, the natural micro crystal graphite that fixed carbon content is 99.9%, its granularity≤40 μ m.Described MCMB is through slight preoxidation, granularity≤20 μ m.Described binding agent is emulsified bitumen, 70 DEG C of pitch softening points, described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen, after having divided, filter unnecessary liquid, dry at 100 DEG C, moisture content is evaporated completely, the product that is uniformly mixed, is ground into the powder of granularity≤3mm;
Second step, adopts extrusion molding to produce moulding graphite green compact, 140 DEG C of extrusion moldings, blank Φ 100 × 300 (mm) to the even mixed powder of gained aggregate and binding agent.
The 3rd step, carries out roasting to moulding graphite green compact, and maturing temperature is 1200 DEG C, roasting time 100 hours;
The 4th step, baked goods are carried out to one time to be flooded and re-baking, when dipping, first preheating 5 hours at 200 DEG C of sample, again impregnating autoclave is vacuumized reach≤0.02MPa, pour into the pitch of melting, under 1.0MPa pressure, flood, impregnated sample is re-baking at 1200 DEG C, roasting time 30 hours.
Gained graphite product: volume density 1.72g/cm
3, degree of graphitization 82%, anisotropic index α=1.12, folding strength 44MPa.
Embodiment tetra-
A kind of synthetic graphite goods of making binding agent with emulsified bitumen of the present embodiment, its raw material comprises binding agent and aggregate, and the mass ratio of binding agent and aggregate is 0.4: 1, and the component of described aggregate is: natural micro crystal graphite accounts for 100% of aggregate quality; Described micro crystal graphite is purified natural micro crystal graphite, and fixed carbon content is 99.9%, granularity≤10 μ m.Described binding agent is emulsified bitumen, 90 DEG C of pitch softening points, and actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen.
A kind of preparation method who makes the synthetic graphite goods of binding agent with emulsified bitumen of the present embodiment, comprises the following steps:
The first step, the binding agent that is 0.4: 1 by actual mass ratio and aggregate at room temperature, are placed in stirrer and evenly mix, and the component of described aggregate is: natural micro crystal graphite accounts for 100% of aggregate quality; Described micro crystal graphite is purified natural micro crystal graphite, raw ore after chemistry or physical method are purified, the natural micro crystal graphite that fixed carbon content is 99.9%, its granularity≤10 μ m.Described binding agent is emulsified bitumen, 90 DEG C of pitch softening points, described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen, after having divided, filter unnecessary liquid, dry at 100 DEG C, moisture content is evaporated completely, the product that is uniformly mixed, is ground into the powder of granularity≤4mm;
Second step adopts isostatic pressing to produce moulding graphite green compact, forming pressure 200MPa, blank Φ 70 × 80 (mm) to the even mixed powder of gained aggregate and binding agent;
The 3rd step, carries out roasting to moulding graphite green compact, and maturing temperature is 800 DEG C, roasting time 50 hours;
The 4th step, baked goods are carried out to 2 times to be flooded and re-baking, when dipping, first preheating 4 hours at 200 DEG C of sample, again impregnating autoclave is vacuumized reach≤0.02MPa, pour into the pitch of melting, under 0.3MPa pressure, flood, impregnated sample is re-baking at 1000 DEG C, roasting time 18 hours;
The 5th step, carries out graphitization processing to the goods that complete dipping and re-baking, and graphitization processing temperature is 2200 DEG C, 20 days used times.
Gained graphite product: volume density 1.85g/cm
3, degree of graphitization g=90%, anisotropic index α=1.03, folding strength 50MPa.
Embodiment five
A kind of synthetic graphite goods of making binding agent with emulsified bitumen of the present embodiment, its raw material comprises binding agent and aggregate, the mass ratio of binding agent and aggregate is 0.05: 1, the component of described aggregate is: MCMB accounts for 100% of aggregate quality, described MCMB is through preoxidation, its granularity≤30 μ m.Described binding agent is emulsified bitumen, 90 DEG C of pitch softening points, and described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen.
A kind of preparation method who makes the synthetic graphite goods of binding agent with emulsified bitumen of the present embodiment, comprises the following steps:
The first step, the binding agent that is 0.05: 1 by actual mass ratio and preoxidation MCMB are at room temperature, being placed in stirrer evenly mixes, the component of described aggregate is: MCMB accounts for 100% of aggregate quality, described MCMB is through preoxidation, its granularity≤30 μ m, described binding agent is emulsified bitumen, 90 DEG C of pitch softening points, described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen, after having divided, filter unnecessary liquid, dry at 120 DEG C, moisture content is evaporated completely, product is uniformly mixed, be ground into the powder of granularity≤5mm,
Second step, adopts isostatic pressing to produce moulding graphite green compact, forming pressure 200MPa, blank Φ 70 × 90 (mm) to the even mixed powder of gained aggregate and binding agent;
The 3rd step, carries out roasting to moulding graphite green compact, and maturing temperature is 1000 DEG C, roasting time 50 hours;
The 4th step, baked goods are carried out to 1 time to be flooded and re-baking, when dipping, first preheating 4 hours at 200 DEG C of sample, again impregnating autoclave is vacuumized reach≤0.02MPa, pour into the pitch of melting, impregnation pressure 0.8MPa, impregnated goods are re-baking at 1000 DEG C, roasting time 18 hours;
The 5th step, carries out graphitization processing to the goods that complete dipping and re-baking, and graphitization processing temperature is 2800 DEG C, 12 days used times.
Gained graphite product: volume density 1.87g/cm
3, degree of graphitization g=89%, anisotropic index α=1.00.
Embodiment six
A kind of synthetic graphite goods of making binding agent with emulsified bitumen of the present embodiment, its raw material comprises binding agent and aggregate, the mass ratio of binding agent and aggregate is 0.4: 1, the component of described aggregate is: secondary Jiao accounts for 100% of aggregate quality, described secondary Jiao is first by the pitch coke elder generation and pitch kneading of maximum particle diameter 0.02-0.15mm, the thickener forming adopts vibratory compaction to form raw product, after 1000 DEG C of roastings, be ground into again the particle of the about 1mm of particle diameter, described binding agent is emulsified bitumen, 100 DEG C of pitch softening points, described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen.
A kind of preparation method who makes the synthetic graphite goods of binding agent with emulsified bitumen of the present embodiment, comprises the following steps:
The first step, the binding agent that is 0.4: 1 by actual mass ratio and secondary Jiao are at room temperature, being placed in stirrer evenly mixes, the component of described aggregate is: secondary Jiao accounts for 100% of aggregate quality, described secondary Jiao is first by the pitch coke elder generation and pitch kneading of maximum particle diameter 0.02-0.15mm, the thickener forming adopts vibratory compaction to form raw product, after 1000 DEG C of roastings, be ground into again the particle of the about 1mm of particle diameter, described binding agent is emulsified bitumen, 100 DEG C of pitch softening points, described actual binding agent quality is the actual pitch phase quality containing in emulsified bitumen, after having divided, filter unnecessary liquid, dry at 150 DEG C, moisture content is evaporated completely, product is uniformly mixed, be ground into the powder of granularity≤3mm,
Second step, adopts isostatic pressing to produce moulding graphite green compact, forming pressure 200MPa, blank Φ 70 × 90 (mm) to the even mixed powder of gained aggregate and binding agent.
The 3rd step, carries out roasting to goods, and maturing temperature is at 1000 DEG C, roasting time 50 hours;
The 4th step, baked goods are carried out to 2 times to be flooded and re-baking, when dipping, first preheating 5 hours at 200 DEG C of sample, again impregnating autoclave is vacuumized reach≤0.02MPa, pour into the pitch of melting, under 1.5MPa pressure, flood, impregnated goods are at 1000 DEG C of re-bakings, roasting time 18 hours;
The 5th step, carries out graphitization processing to the goods that complete dipping and re-baking, and graphitization processing temperature is 3000 DEG C, 10 days used times.
Gained graphite product: volume density 1.85g/cm
3, anisotropic index α=1.02, folding strength 32MPa.
In sum, the present invention has and can at room temperature operate, and consumption of binder is few, mixes technique environmental protection with aggregate; Aggregate range of choice is large, and the limitation for molding of preparation is little; The isotropic behavior high of goods, thereby can in high-performance graphite product is produced, promote.
Claims (6)
1. make the synthetic graphite goods of binding agent with emulsified bitumen for one kind, its raw material comprises binding agent and aggregate, it is characterized in that: binding agent is (0.05-0.70) with the actual mass ratio of aggregate: 1, described aggregate is: one or more in refinery coke, pitch coke, secondary Jiao, natural micro crystal graphite, MCMB or graphite returns; In the time that aggregate is two or more, different aggregates do not have limited proportion each other; In the time that the main body of aggregate is natural micro crystal graphite, natural micro crystal graphite accounts for the 50-100% of aggregate quality, and its clout is one or more in pitch coke, refinery coke, secondary Jiao, MCMB or graphite returns, and there is no each other limited proportion; Described binding agent is emulsified bitumen, pitch solid phase weight content 40-70%, pitch softening point 60-100 DEG C.
2. synthetic graphite goods according to claim 1, is characterized in that: its isotropy degree α≤1.15, are specially: distinguish the goods of compression molding, extrusion molding, isotropy degree α≤1.15 by forming method; Vibratory compaction and isostatic pressing goods, α≤1.10; Distinguish secondary Jiao, natural micro crystal graphite, MCMB resulting product, α≤1.10 by aggregate type; Add refinery coke, pitch coke and other aggregate resulting product α≤1.15.
3. a method of preparing synthetic graphite goods described in claim 1 or 2, is characterized in that: using emulsified bitumen as binding agent, comprise the following steps:
The first step, be (0.05-0.70) by actual mass ratio: 1 emulsified bitumen mixes with aggregate: the actual mass of binding agent calculates according to the solid phase weight content of emulsified bitumen, emulsified bitumen as required can thin up be 1～10 times of emulsified bitumen weight, be adjusted to required viscosity, then emulsified bitumen and aggregate are placed in to stirrer, mix, after emulsified bitumen has divided, filter unnecessary liquid, dry at 50-150 DEG C, moisture content is evaporated completely, and the product that is uniformly mixed, is ground into the powder of granularity≤5mm;
Described emulsified bitumen, pitch weight content 40-70%, pitch softening point 60-100 DEG C;
Described aggregate is one or more in refinery coke, pitch coke, secondary Jiao, natural micro crystal graphite, MCMB or graphite returns, in the time that the main body of aggregate is natural micro crystal graphite, natural micro crystal graphite accounts for the 50-100% of aggregate quality, its clout is one or more in pitch coke, refinery coke, secondary Jiao, MCMB or graphite returns, and there is no each other limited proportion;
Second step, adopts compression molding, extrusion molding, vibratory compaction or isostatic pressing to produce moulding graphite green compact to the even mixed powder of gained aggregate and binding agent;
The 3rd step, carries out roasting to moulding graphite green compact, maturing temperature 800-1200 DEG C, roasting time 10-900 hour;
The 4th step, baked moulding graphite green compact are carried out to dipping and the re-baking of 1-3 time, when dipping, first moulding graphite green compact are carried out to 200 DEG C of preheatings, time 3-5 hour, then impregnating autoclave is vacuumized, pressure≤0.02MPa, adds the pitch of melting, under 0.3-1.5MPa pressure, flood, impregnated goods are at 800-1000 DEG C of re-baking, roasting time 10-100 hour, and the re-baking temperature of each time is identical or different;
The 5th step, the goods that complete dipping and re-baking are carried out to graphitization processing, graphitization processing temperature is 2200-3000 DEG C, 10 days to 20 days used time, if aggregate main body is natural graphite or graphite returns and fixed carbon content >=98%, natural graphite or graphite returns are in aggregate when shared mass ratio >=50%, in the time requiring the folding strength of isotropic graphite product to be greater than 50MPa, can not carry out graphitization processing, last re-baking temperature is 900-1200 DEG C.
4. method according to claim 3, is characterized in that: the raw material of the emulsified bitumen described in the first step is soft pitch, mid-temperature pitch, hard pitch or modified pitch; Coal-tar pitch or petroleum pitch.
5. method according to claim 3, is characterized in that: the emulsified bitumen carbonization yield described in the first step is 15-50%, and grain diameter is 1-3 μ m.
6. method according to claim 3, it is characterized in that: the natural micro crystal graphite described in the first step is purified natural micro crystal graphite, be raw ore after chemistry or physical method are purified, the natural micro crystal graphite that fixed carbon content is 90-99.99%, its granularity is 1-150 μ m.
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