CN113046023A - Preparation method and application of environment-friendly asphalt - Google Patents
Preparation method and application of environment-friendly asphalt Download PDFInfo
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- CN113046023A CN113046023A CN202110266248.2A CN202110266248A CN113046023A CN 113046023 A CN113046023 A CN 113046023A CN 202110266248 A CN202110266248 A CN 202110266248A CN 113046023 A CN113046023 A CN 113046023A
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- 239000010426 asphalt Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 44
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 36
- 239000011593 sulfur Substances 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012065 filter cake Substances 0.000 claims abstract description 18
- 238000004939 coking Methods 0.000 claims abstract description 15
- 239000007770 graphite material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 230000005496 eutectics Effects 0.000 claims abstract description 12
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910021383 artificial graphite Inorganic materials 0.000 claims abstract description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 23
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical group C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 17
- 229960001231 choline Drugs 0.000 claims description 17
- 239000011300 coal pitch Substances 0.000 claims description 13
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011301 petroleum pitch Substances 0.000 claims description 10
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- PJRBEVRZDCTQSN-UHFFFAOYSA-N 2-hydroxybutanedioic acid;hydrochloride Chemical compound Cl.OC(=O)C(O)CC(O)=O PJRBEVRZDCTQSN-UHFFFAOYSA-N 0.000 claims description 6
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical group CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 4
- YOZJRGMOPGMPAC-UHFFFAOYSA-M [Br-].C(CCC)[N+](CCCC)(CCCC)CCCC.C(=O)O Chemical compound [Br-].C(CCC)[N+](CCCC)(CCCC)CCCC.C(=O)O YOZJRGMOPGMPAC-UHFFFAOYSA-M 0.000 claims description 3
- BPACUFRWYJXUJV-UHFFFAOYSA-M [Br-].C(CCC)[N+](CCCC)(CCCC)CCCC.C(C1=CC=CC=C1)(=O)O Chemical compound [Br-].C(CCC)[N+](CCCC)(CCCC)CCCC.C(C1=CC=CC=C1)(=O)O BPACUFRWYJXUJV-UHFFFAOYSA-M 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- RHOPUUFLVKWWFP-UHFFFAOYSA-N 2-phenylacetic acid;hydrochloride Chemical compound Cl.OC(=O)CC1=CC=CC=C1 RHOPUUFLVKWWFP-UHFFFAOYSA-N 0.000 claims description 2
- CUUNVSSTSXLCLH-UHFFFAOYSA-N 2-phenylpropanoic acid;hydrochloride Chemical compound Cl.OC(=O)C(C)C1=CC=CC=C1 CUUNVSSTSXLCLH-UHFFFAOYSA-N 0.000 claims description 2
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N Chloride-Phenylacetic acid Natural products ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 claims description 2
- JXHYCCGOZUGBFD-UHFFFAOYSA-N benzoic acid;hydrochloride Chemical compound Cl.OC(=O)C1=CC=CC=C1 JXHYCCGOZUGBFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- SNBDGFZQPKCZTO-UHFFFAOYSA-N propanedioic acid;hydrochloride Chemical compound Cl.OC(=O)CC(O)=O SNBDGFZQPKCZTO-UHFFFAOYSA-N 0.000 claims description 2
- HJJPJSXJAXAIPN-UHFFFAOYSA-N arecoline Chemical compound COC(=O)C1=CCCN(C)C1 HJJPJSXJAXAIPN-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 239000000779 smoke Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000010926 purge Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910002804 graphite Inorganic materials 0.000 description 16
- 239000010439 graphite Substances 0.000 description 16
- 239000011295 pitch Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 7
- 239000011305 binder pitch Substances 0.000 description 6
- 239000011294 coal tar pitch Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012615 aggregate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011311 coal-based needle coke Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J195/00—Adhesives based on bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention belongs to the technical field of asphalt deep processing, and particularly discloses a preparation method of environment-friendly asphalt, which comprises the following steps of uniformly mixing raw materials at 80-100 ℃, mixing the mixed raw materials with an oxidant and a eutectic solvent, keeping the mixture at 25-100 ℃ for 0-48 h, gradually heating, keeping the mixture at 250 ℃ for 0-48 h, after the reaction is finished, purging the mixture with nitrogen to cool, separating the solvent through vacuum filtration, separating sulfur and nitrogen components along with the solvent, washing a filter cake with ethanol for multiple times, drying the filter cake to obtain the environment-friendly asphalt, wherein the coking value and the softening point of the obtained asphalt are proper, and meanwhile, the amount of asphalt smoke generated in the high-temperature treatment process is less and the toxicity is lower; the prepared environment-friendly asphalt is applied to the artificial graphite material adhesive, the permeability of the adhesive is good, the coking value is high, the porosity of a product can be reduced by using the adhesive asphalt, the strength of the graphite material is improved, and the service life of the product is prolonged.
Description
Technical Field
The invention belongs to the technical field of asphalt deep processing, and particularly relates to a preparation method of low-sulfur low-nitrogen environment-friendly asphalt.
Background
The binder pitch is an important raw material for preparing artificial graphite materials such as graphite electrodes, high-purity graphite and the like, and the performance of the binder pitch is very important for the quality and the performance of the artificial graphite materials. In order to obtain a binder pitch with proper rheological properties, currently industrially used binder pitches are usually medium-temperature pitches, medium-temperature modified pitches or coal pitches doped with anthracene oil. These adhesives have the following problems during use:
the phenomenon of "flatulence" is obvious. Similar to aggregate, sulfur and nitrogen contents in the sticky coke can also generate a phenomenon of 'ballooning' in the graphitization process, and at the moment, irreversible cracks are generated on a graphite product, so that the quality of graphite preparation is reduced. In the roasting process of the asphalt, the coking shrinkage of the asphalt forms sticky coke, part of nitrogen-containing compounds is not changed or converted into ammonia, and most of nitrogen remains in the coke; a portion of the sulfur is evolved with the gas as hydrogen sulfide and a portion is distributed in the coke as organic sulfur compounds. When the temperature rises to above 1400 ℃, namely during the graphitization process, elements such as hydrogen, sulfur, nitrogen and the like are expressed as H2，H2S，N2，NH3And the nitrogen is mainly released at 1400-1900 ℃, the sulfur is released in a concentrated manner at 1700-2100 ℃, and the pore wall of the coke in a plastic state is subjected to the pressure of the exhausted gas, so that the volume expands, and the physical and chemical properties of the graphite product are reduced. The binder accounts for 25-40% of the paste produced by the graphite material, and although the roasting treatment can reduce the content of part of sulfur and nitrogen, part of sulfur and nitrogen elements in the sticky coke formed by roasting still remain.
In order to reduce the cracks of graphite materials, researches are mainly carried out on the aspects of controlling the graphitization heating rate and reducing the sulfur and nitrogen content of aggregates at present, and few reports are made on the aspect of reducing the sulfur and nitrogen content in the binder asphalt.
In the prior art, patent publication No. CN101880542 proposes "a method for removing organic sulfur from coal pitch" by using a surfactant and an organic solvent to increase the dispersion and emulsification degree of an oxidant in a coal pitch system, improve the effect of oxidizing organic sulfur in coal pitch by the oxidant, extract oxidized sulfides by a mixed extract composed of methanol and dilute alkali, and further remove the sulfur-containing extract by vacuum filtration to realize deep desulfurization. The method needs a large amount of volatile organic solvent, has large investment and is easy to cause environmental pollution, and the method does not relate to the research on removing organic nitrogen in the coal pitch.
And secondly, the asphalt smoke discharge amount is large in the heat treatment process, and the asphalt can generate the processes of melt migration, thermal decomposition, thermal polycondensation, coking shrinkage and graphitization in the preparation process of the artificial graphite material. A large amount of asphalt fumes and dust are generated at each heat treatment stage. The asphalt smoke contains a large amount of anthracene, phenanthrene, pyrene and other polycyclic aromatic hydrocarbon components, wherein carcinogenic substances 3, 4 benzopyrene are 2.5-3.5%. Studies have shown that when the treatment temperature is below 350 ℃, the volatiles are mainly composed of light components in the coal pitch with boiling points below 400 ℃, and only a small portion comes from the decomposition of its high molecular weight components. And when the temperature is heated to 650 ℃, the volatile components mainly consist of the high PAH component and the high PAH decomposition product of the coal pitch. Therefore, the discharge amount of asphalt smoke can be reduced by reducing the content of low molecular components (boiling point < 400 ℃) in the coal asphalt. However, this results in deterioration of rheological properties of coal pitch, deterioration of the effect of impregnating aggregate at kneading, and failure to effectively reduce the amount of asphalt smoke discharged during high-temperature heat treatment (> 650 ℃).
In conclusion, the conventional binder pitch can generate a great deal of pitch smoke and H in the preparation process of the graphite material2S、NH3The graphite material generates a large amount of cracks, the strength of the graphite material is reduced, the working environment is polluted, the environment-friendly treatment cost is increased, and the health of field operators is influenced.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for preparing low-sulfur low-nitrogen environment-friendly asphalt and application of the low-sulfur low-nitrogen environment-friendly asphalt prepared by the method in artificial graphite material binders.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the preparation method of the environment-friendly asphalt comprises the following steps:
firstly, uniformly mixing the raw materials at 80-100 ℃, wherein the mass ratio of the raw materials is as follows: 30-50% of coal pitch, 0-45% of petroleum pitch and 0-50% of anthracene oil.
And secondly, mixing the mixed raw material in the step one with an oxidant and a eutectic solvent, keeping the mixture at 25-100 ℃ for 0-48 h, gradually heating the mixture, keeping the mixture at 200-250 ℃ for 0-48 h, after the reaction is finished, blowing the mixture to be cooled by using nitrogen, separating the solvent by vacuum filtration, introducing sulfur and nitrogen components into the solvent to be separated, washing the filter cake for multiple times by using ethanol, and drying the filter cake to obtain the environment-friendly asphalt.
In the second step, the mass ratio of the mixed raw materials to the oxidant is 1: 1-30, wherein the mass ratio of the mixed raw materials to the eutectic solvent is 1: 1-20.
Wherein the eutectic solvent is subjected to CCl4The back extraction can be repeatedly used.
The eutectic solvent is choline chloride-organic acid, and the choline chloride-organic acid is choline chloride-benzoic acid, or choline chloride-phenylacetic acid, or choline chloride-phenylpropionic acid, or choline chloride-malonic acid, or choline chloride-malic acid, etc.
The eutectic solvent is tetrabutylammonium bromide-organic acid, and the tetrabutylammonium bromide-organic acid is tetrabutylammonium bromide-formic acid or tetrabutylammonium bromide-benzoic acid and the like.
The oxidant is a mixture of potassium ferrate and 10-13% of sodium hypochlorite, and the mass ratio of the potassium ferrate to the sodium hypochlorite is 1: 5-20, and the oxidant is prepared in use in the actual use process.
The coal pitch is one or the combination of any more of low-temperature pitch, medium-temperature pitch, high-temperature pitch and modified pitch; the petroleum asphalt is one or the combination of any more of straight-run asphalt, oxidized asphalt, emulsified asphalt and modified asphalt.
The softening point of the environment-friendly asphalt is 90-120 ℃, the coking value is more than or equal to 55 percent, the beta resin content is more than or equal to 20 percent, the sulfur removal rate is more than or equal to 95 percent, and the nitrogen removal rate is more than or equal to 85 percent
Use of the environmentally friendly asphalt prepared according to claim 1 as a binder for artificial graphite materials.
Compared with the prior art, the invention has the following specific beneficial effects:
firstly, the invention takes the mixture of coal pitch, petroleum pitch and anthracene oil as raw materials to carry out oxidation modification, which is beneficial to reducing carcinogenic substances such as polycyclic aromatic hydrocarbon with the boiling point lower than 350 ℃ in the binder pitch, and compared with the method which only uses the coal pitch as the binder, the invention mixes the pitch with lower toxicity such as pitch formed by the coal pitch, the petroleum pitch and the anthracene oil to obtain the pitch with proper coking value and softening point, and simultaneously, the invention has less pitch smoke generated in the high-temperature treatment process (more than 650 ℃, such as roasting and graphitization treatment processes) and lower toxicity.
Secondly, the eutectic solvent has the functions of both the solvent and the catalyst, the desulfurization effect is more than 95 percent, the denitrification effect is more than 85 percent, and the eutectic solvent is easy to separate from the asphalt after the reaction.
The invention adopts ferrate and sodium hypochlorite to carry out oxidation reaction, the oxidant is cheap and easy to obtain, the oxidation effect is good, and a small amount of Fe is generated as a byproduct in the reaction2O3And the asphalt is uniformly distributed in the asphalt without separation. In the production of artificial graphite, in order to inhibit the "ballooning" of the aggregate during graphitization, a proper amount of ballooning inhibitor (such as iron oxide, cobalt oxide, nickel oxide, etc.) is usually added in the mixing process. The by-product of the ferrate reaction can be used as a ballooning inhibitor of the aggregate in the graphitization production, is beneficial to reducing the kneading time in the production process of the graphite material, and has better inhibition effect on the ballooning of the framework material.
The invention adopts a one-pot preparation method, temperature programming and two-step temperature-raising oxidation treatment are carried out, the reaction condition is mild, and the prepared environment-friendly asphalt is used as a graphite material binder and has good permeability, high coking value, low porosity of the product, high strength and long service life.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first embodiment is as follows: 100g of coal tar pitch, 75g of petroleum pitch and 25g of anthracene oil are uniformly mixed at 80 ℃ to prepare a raw material mixture, and the sulfur content and the nitrogen content of the mixture are respectively 1.1% and 0.6% according to tests. 4g of potassium ferrate is dissolved in 200g of 13% sodium hypochlorite solution to prepare an oxidant. Mixing the raw material mixture with 204g of oxidant and 200g of choline chloride-malic acid, keeping the mixture at 80 ℃ for 5h, gradually heating the mixture, keeping the mixture at 200 ℃ for 24h, blowing the mixture to cool by using nitrogen after the reaction is finished, separating the solvent by vacuum filtration, separating sulfur and nitrogen components from the solvent, washing the filter cake with ethanol for multiple times, and drying the filter cake to obtain the binder asphalt. The obtained asphalt product can be used as a graphite electrode material binder, and has a softening point of 96 ℃, a coking value of 55%, a beta resin content of 20.2%, a sulfur removal rate of 97.2% and a nitrogen removal rate of 86.4%.
Example two: 100g of coal tar pitch, 75g of petroleum pitch and 25g of anthracene oil are uniformly mixed at 80 ℃ to prepare a raw material mixture, and the sulfur content and the nitrogen content of the mixture are respectively 1.1% and 0.6% according to tests. 4g of potassium ferrate is dissolved in 200g of 13% sodium hypochlorite solution to prepare an oxidant. Mixing the raw material mixture with 204g of oxidant and 200g of choline chloride-malic acid, keeping the mixture at 80 ℃ for 5h, gradually heating the mixture, keeping the mixture at 200 ℃ for 48h, blowing the mixture to cool by using nitrogen after the reaction is finished, separating the solvent by vacuum filtration, separating sulfur and nitrogen components from the solvent, washing the filter cake with ethanol for multiple times, and drying the filter cake to obtain the binder asphalt. The obtained asphalt product can be used as a graphite electrode material binder, and has a softening point of 98 ℃, a coking value of 57%, a beta resin content of 20.8%, a sulfur removal rate of 97.3% and a nitrogen removal rate of 86.6%.
Example three: 100g of coal tar pitch, 75g of petroleum pitch and 25g of anthracene oil are uniformly mixed at 80 ℃ to prepare a raw material mixture, and the sulfur content and the nitrogen content of the mixture are respectively 1.1% and 0.6% according to tests. 4g of potassium ferrate is dissolved in 204g of 13% sodium hypochlorite solution to prepare an oxidant I. Mixing the raw material mixture with 150g of oxidant I and 200g of tetrabutylammonium bromide-benzoic acid, keeping the mixture at 80 ℃ for 5 hours, gradually heating the mixture, keeping the mixture at 200 ℃ for 24 hours, blowing the mixture with nitrogen to cool after the reaction is finished, separating the solvent through vacuum filtration, introducing sulfur and nitrogen components into the solvent to be separated, washing the filter cake with ethanol for multiple times, and drying the filter cake to obtain the binder asphalt. The obtained asphalt product can be used as a graphite electrode material binder, and has a softening point of 96 ℃, a coking value of 55%, a beta resin content of 20.3%, a sulfur removal rate of 97.8% and a nitrogen removal rate of 88.7%.
Example four: 100g of coal tar pitch, 75g of petroleum pitch and 25g of anthracene oil are uniformly mixed at 80 ℃ to prepare a raw material mixture, and the sulfur content and the nitrogen content of the mixture are respectively 1.1% and 0.6% according to tests. 4g of potassium ferrate is dissolved in 200g of 13% sodium hypochlorite solution to prepare an oxidant. Mixing the raw material mixture with 204g of oxidant and 200g of choline chloride-malic acid, keeping the mixture at 80 ℃ for 24h, gradually heating the mixture, keeping the mixture at 200 ℃ for 48h, blowing the mixture to cool by using nitrogen after the reaction is finished, separating the solvent by vacuum filtration, separating sulfur and nitrogen components from the solvent, washing the filter cake with ethanol for multiple times, and drying the filter cake to obtain the binder asphalt. The obtained asphalt product can be used as a graphite electrode material binder, and has a softening point of 102 ℃, a coking value of 58%, a beta resin content of 22.5%, a sulfur removal rate of 98.1% and a nitrogen removal rate of 87.3%.
Example five: 100g of coal tar pitch, 75g of petroleum pitch and 25g of anthracene oil are uniformly mixed at 80 ℃ to prepare a raw material mixture, and the sulfur content and the nitrogen content of the mixture are respectively 1.1% and 0.6% according to tests. 4g of potassium ferrate is dissolved in 200g of 13% sodium hypochlorite solution to prepare an oxidant. Mixing the raw material mixture with 204g of oxidant and 200g of tetrabutylammonium bromide-formic acid, keeping the mixture at 80 ℃ for 5h, gradually heating the mixture, keeping the mixture at 200 ℃ and 250 ℃ for 24h, blowing the mixture to cool the mixture by using nitrogen after the reaction is finished, separating the solvent by vacuum filtration, introducing sulfur and nitrogen components into the solvent to be separated, washing the filter cake by using ethanol for multiple times, and drying the filter cake to obtain the binder asphalt. The obtained asphalt product can be used as a graphite electrode material binder, and has a softening point of 97 ℃, a coking value of 56%, a beta resin content of 21.1%, a sulfur removal rate of 97.0% and a nitrogen removal rate of 85.4%.
Example six: 100g of coal tar pitch, 75g of petroleum pitch and 25g of anthracene oil are uniformly mixed at 80 ℃ to prepare a raw material mixture, and the sulfur content and the nitrogen content of the mixture are respectively 1.1% and 0.6% according to tests. 4g of potassium ferrate is dissolved in 200g of 13% sodium hypochlorite solution to prepare an oxidant. Mixing the raw material mixture with 204g of oxidant and 250g of choline chloride-malic acid, keeping the mixture at 80 ℃ for 5h, gradually heating the mixture, keeping the mixture at 200 ℃ and 250 ℃ for 24h, blowing the mixture to cool the mixture by using nitrogen after the reaction is finished, separating the solvent by vacuum filtration, introducing sulfur and nitrogen components into the solvent to be separated, washing the filter cake by using ethanol for multiple times, and drying the filter cake to obtain the binder asphalt. The obtained asphalt product can be used as a graphite electrode material binder, and has a softening point of 95 ℃, a coking value of 55%, a beta resin content of 21.2%, a sulfur removal rate of 98.3% and a nitrogen removal rate of 89.4%.
Comparative example: the softening point of the purchased modified asphalt is 98 ℃, the coking value is 55%, the beta resin content is 18.0%, the sulfur content is 3.2%, and the nitrogen content is 1.6%.
The binder pitch obtained in examples 1 to 6 and the purchased modified pitch were used as binders for ultrahigh-power graphite electrodes, 10kg of coal-based needle coke and 4kg of binders were used, and the ultrahigh-power graphite electrodes were prepared by kneading, molding, baking, dipping, baking, graphitizing and the like according to a conventional preparation process of ultrahigh-power graphite electrodes. The following properties of the electrodes prepared in accordance with the respective examples were measured, as shown in the following table.
The data show that the volume density and the breaking strength of the graphite electrode can be obviously increased by adopting the asphalt as the binder, and the electrical resistivity and the thermal expansion coefficient are lower, so that the requirements of the ultrahigh-power graphite electrode can be met.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included therein.
Claims (7)
1. The preparation method of the environment-friendly asphalt is characterized by comprising the following steps:
firstly, uniformly mixing the raw materials at 80-100 ℃, wherein the mass ratio of the raw materials is as follows: 30-50% of coal pitch, 0-45% of petroleum pitch and 0-50% of anthracene oil;
mixing the mixed raw material in the step one with an oxidant and a eutectic solvent, keeping the mixture at 25-100 ℃ for 0-48 h, gradually heating the mixture, keeping the mixture at 200-250 ℃ for 0-48 h, after the reaction is finished, blowing the mixture to be cooled by using nitrogen, separating the solvent by vacuum filtration, separating sulfur and nitrogen components along with the solvent, washing a filter cake for multiple times by using ethanol, and drying the filter cake to obtain the environment-friendly asphalt;
in the second step, the mass ratio of the mixed raw materials to the oxidant is 1: 1-30, wherein the mass ratio of the mixed raw materials to the eutectic solvent is 1: 1-20.
2. The method for preparing environment-friendly asphalt according to claim 1, wherein the eutectic solvent is choline chloride-organic acids, and the choline chloride-organic acids are choline chloride-benzoic acid, or choline chloride-phenylacetic acid, or choline chloride-phenylpropionic acid, or choline chloride-malonic acid, or choline chloride-malic acid.
3. The method for preparing environment-friendly asphalt according to claim 2, wherein the eutectic solvent is tetrabutylammonium bromide-organic acids, and the tetrabutylammonium bromide-organic acids are tetrabutylammonium bromide-formic acid or tetrabutylammonium bromide-benzoic acid.
4. The method for preparing environment-friendly asphalt according to claim 1, wherein the oxidant is a mixture of potassium ferrate and 10-13% of sodium hypochlorite, and the mass ratio of the potassium ferrate to the sodium hypochlorite is 1: 5-20.
5. The method for preparing the environment-friendly asphalt according to claim 1, wherein the coal asphalt is one or a combination of any of low-temperature asphalt, medium-temperature asphalt, high-temperature asphalt and modified asphalt; the petroleum asphalt is one or the combination of any more of straight-run asphalt, oxidized asphalt, emulsified asphalt and modified asphalt.
6. The method for preparing environment-friendly asphalt according to claim 1, wherein the softening point of the environment-friendly asphalt is 90-120 ℃, the coking value is not less than 55%, the beta resin content is not less than 20%, the sulfur removal rate is not less than 95%, and the nitrogen removal rate is not less than 85%.
7. Use of the environmentally friendly asphalt prepared according to claim 1 as a binder for artificial graphite materials.
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