CN118529718B - Pressed calcined petroleum coke and production method and application thereof - Google Patents
Pressed calcined petroleum coke and production method and application thereof Download PDFInfo
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- 239000002008 calcined petroleum coke Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002006 petroleum coke Substances 0.000 claims abstract description 80
- 239000010426 asphalt Substances 0.000 claims abstract description 49
- 239000011230 binding agent Substances 0.000 claims abstract description 33
- 229920001690 polydopamine Polymers 0.000 claims abstract description 31
- 238000003825 pressing Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 23
- 239000004917 carbon fiber Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001721 carbon Chemical class 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000001007 puffing effect Effects 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000010439 graphite Substances 0.000 abstract description 6
- 229910002804 graphite Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 239000000292 calcium oxide Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/005—After-treatment of coke, e.g. calcination desulfurization
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Coke Industry (AREA)
Abstract
The invention provides compacted and calcined petroleum coke and a production method and application thereof, and belongs to the technical field of petroleum coke. Comprising the following steps: s1, preparing puffed petroleum coke; s2, preparing polydopamine modified carbon fibers; s3, preparing an asphalt binder; s4, pressing; s5, calcining. The pressed and calcined petroleum coke prepared by the method has the advantages of high density, small porosity, small resistivity, good adhesiveness, good mechanical property, simple method, mild condition, balanced and stable quality, can be used for producing carbon products such as graphitized electrodes, prebaked anodes for aluminum electrolysis, self-baking anode pastes, cathode tank cold rammed carbon materials, cathode pastes, pure graphitized crucibles, graphite armatures and the like, and has wide application prospects.
Description
Technical Field
The invention relates to the technical field of petroleum coke, in particular to compacted and calcined petroleum coke, and a production method and application thereof.
Background
The residue, residual oil or petroleum asphalt after petroleum distillation is coked at high temperature to obtain pre-forging petroleum coke, which is calcined to obtain calcined petroleum coke. The calcined petroleum coke can be used for producing carbon products such as graphitized electrodes, prebaked anodes for aluminum electrolysis, self-baked anode pastes, cathode tank cold stamping carbon materials, cathode pastes, pure graphitized crucibles, graphite armatures and the like.
The volume density of the calcined petroleum coke produced at present is generally 0.9-1.1g/cm 3, the true density is 2.0-2.10g/cm 3, the apparent porosity is 40-60%, the water absorption is 30-50%, because the volume density is low, the compressive strength and the conductivity are poor, a large amount of asphalt binder is consumed in the process of producing the carbon product, the coking value of asphalt is only 50%, and the quality of the carbon product is finally affected. The performance index of petroleum coke is determined by the production and processing method, and the existing method is that the petroleum coke before forging is directly calcined by a pot calciner to become calcined petroleum coke, and then crushed to the required granularity. The method is simple, but the product index fluctuation is serious, and the quality of the carbon product is reduced because the method can not meet the requirement. In order to improve the quality of carbon products, there is a need for a petroleum coke product with high bulk density, high true density and good electrical conductivity, and a method for producing the same.
The Chinese patent document CN1227327C discloses compacted and calcined petroleum coke and a production method thereof, although the production method of the compacted and calcined petroleum coke comprises screening classification, ball pressing, screening, calcination and oil immersion. The quality of the pressed and calcined petroleum coke product is balanced and stable, and the technical indexes of products produced successively are consistent. However, the pressed and calcined petroleum coke still has the problems of poor mechanical properties and the like.
Disclosure of Invention
The invention aims to provide pressed and calcined petroleum coke, and a production method and application thereof, which have the advantages of high density, small porosity, small resistivity, good adhesion, good mechanical property, simple method, mild condition, balanced and stable quality, can be used for producing carbon products such as graphitized electrodes, prebaked anodes for aluminum electrolysis, self-baked anode paste, cathode tank cold stamping carbon materials, cathode paste, pure graphitized crucibles, graphite armatures and the like, and has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a production method of compacted and calcined petroleum coke, which comprises the following steps:
S1, preparing puffed petroleum coke: crushing petroleum coke, mixing with CaO, ball milling, adding the crushed petroleum coke into hydrogen peroxide, heating, stirring, reacting, filtering, adding the mixed acid into the mixed acid, stirring, reacting, filtering, washing, drying, and puffing at a low temperature to obtain puffed petroleum coke, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, the volume ratio is 1:0.7-1.2, the temperature of the low temperature puffing treatment is 150-250 ℃, the time is 1-3h, and the mass ratio of the petroleum coke to the CaO is 10:1-2;
S2, preparing polydopamine modified carbon fibers: adding carbon fiber into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, centrifuging, washing, and drying to obtain polydopamine modified carbon fiber, wherein the mass ratio of the carbon fiber to the dopamine hydrochloride to the catalyst is 10:2-3:0.1-0.2;
S3, preparing an asphalt binder: adding polydopamine modified carbon fiber into asphalt, and uniformly stirring and mixing to obtain an asphalt binder, wherein the mass ratio of polydopamine modified carbon fiber to asphalt is 3-5:10;
s4, pressing: uniformly mixing the puffed petroleum coke and the asphalt binder, and pressing the mixture into blocks by a ball pressing machine to obtain pressed petroleum coke, wherein the mass ratio of the puffed petroleum coke to the asphalt binder is 10:2-3;
S5, calcining: calcining the compacted petroleum coke to obtain the compacted and calcined petroleum coke.
As a further improvement of the invention, the temperature of the heating and stirring reaction in the step S1 is 40-50 ℃, the time is 30-40min, and the time of the stirring reaction is 30-50min.
As a further improvement of the invention, the solid-to-liquid ratio of the petroleum coke and the hydrogen peroxide in the step S1 is 1g:5-7mL, and the solid-to-liquid ratio of the petroleum coke and the mixed acid is 1g:3-5mL, wherein the concentration of the hydrogen peroxide is 8-12wt%.
As a further improvement of the invention, the catalyst in the step S2 is Tris-HCl solution with pH=8.5-9.5, and the temperature of the heating and stirring reaction is 40-50 ℃ for 2-3h.
As a further improvement of the invention, the stirring and mixing time in the step S3 is 20-40min.
As a further improvement of the invention, the hydraulic thrust of the pressing roller of the ball press in the step S4 is 80-100 tons.
As a further improvement of the invention, the calcination in step S5 is carried out at a temperature of 1100-1300 ℃ for a time of 1-3 hours.
As a further improvement of the invention, the method specifically comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10 parts by weight of petroleum coke, mixing and ball-milling with 1-2 parts by weight of CaO, adding into 8-12wt% of hydrogen peroxide, heating to 40-50 ℃ with the solid-liquid ratio of 1g:5-7mL, stirring for reaction for 30-40min, filtering, and adding into mixed acid with the solid-liquid ratio of 1g:3-5mL, stirring and reacting for 30-50min, filtering, washing, drying, puffing at 150-250 ℃ for 1-3h to obtain puffed petroleum coke;
the mixed acid is mixed solution of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 1:0.7-1.2;
S2, preparing polydopamine modified carbon fibers: adding 10 parts by weight of carbon fiber into water, adding 2-3 parts by weight of dopamine hydrochloride and 0.1-0.2 part by weight of catalyst, heating to 40-50 ℃, stirring and reacting for 2-3 hours, centrifuging, washing and drying to obtain polydopamine modified carbon fiber;
the catalyst is Tris-HCl solution with pH=8.5-9.5;
S3, preparing an asphalt binder: adding 3-5 parts by weight of polydopamine modified carbon fiber into 10 parts by weight of asphalt, and stirring and mixing for 20-40min to prepare an asphalt binder;
S4, pressing: uniformly mixing 10 parts by weight of puffed petroleum coke and 2-3 parts by weight of asphalt binder, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of 80-100 tons to obtain compacted petroleum coke;
S5, calcining: heating the compacted and calcined petroleum coke to 1100-1300 ℃ and calcining for 1-3h to obtain the compacted and calcined petroleum coke.
The invention further protects the compacted and calcined petroleum coke prepared by the production method.
The invention further protects the application of the compacted and calcined petroleum coke in preparing carbon products.
The invention has the following beneficial effects:
petroleum coke has low price and huge profit because of being capable of being effectively utilized. But its high sulfur content limits its use. Wherein, the existence form of sulfur is stable, and the sulfur is distributed in a carbon skeleton and an aromatic ring and is difficult to remove.
According to the invention, calcium oxide and crushed petroleum coke are subjected to mixed ball milling treatment, ca is intercalated in the petroleum coke, the structure of the petroleum coke is pre-regulated, sulfide is fully exposed, the graphite microcrystalline structure in the petroleum coke is loosened, the contact efficiency of the sulfide and oxidant hydrogen peroxide is improved, the desulfurization of the oxidation reaction is facilitated, the condition is mild, the byproduct is water, the mixed acid (concentrated sulfuric acid and concentrated nitric acid) with strong oxidizing capability is treated, on one hand, the acid can react with alkaline substance Ca intercalated in the petroleum coke, the rapid puffing effect can be achieved, the interlayer spacing of the internal graphite microcrystalline structure is increased, on the other hand, the mixed acid also has good oxidizing property, the sulfide can be further oxidized, the removal of the sulfide is facilitated, and meanwhile, the microstructure of the petroleum coke is more fluffy, so that the permeation and adhesion of an asphalt binder are facilitated, the density of the prepared densely calcined petroleum coke is greatly improved, the porosity is reduced, and the resistivity is obviously reduced.
According to the asphalt binder disclosed by the invention, the polydopamine surface coating modified carbon fiber is added, so that on one hand, the mechanical property of the prepared compacted calcined petroleum coke can be obviously improved, meanwhile, the high viscosity of polydopamine improves the adhesiveness of asphalt to petroleum coke and the compatibility of the carbon fiber, the distribution property of asphalt is improved, the agglomeration is reduced, the density of the compacted calcined petroleum coke is improved, and the porosity is reduced.
The pressed and calcined petroleum coke prepared by the method has the advantages of high density, small porosity, small resistivity, good adhesiveness, good mechanical property, simple method, mild condition, balanced and stable quality, can be used for producing carbon products such as graphitized electrodes, prebaked anodes for aluminum electrolysis, self-baking anode pastes, cathode tank cold rammed carbon materials, cathode pastes, pure graphitized crucibles, graphite armatures and the like, and has wide application prospects.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Petroleum coke with sulfur content of 2.2-2.7wt% is available from Tianjin Mingxin Tai petrochemical Co.
Example 1
The embodiment provides a production method of compacted and calcined petroleum coke, which specifically comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10g of petroleum coke, mixing with 1g of CaO, ball milling, adding 50mL of 8wt% hydrogen peroxide, heating to 40 ℃, stirring for reaction for 30min, filtering, adding 30mL of mixed acid, stirring for reaction for 30min, filtering, washing, drying, and puffing at 150 ℃ for 1h to obtain puffed petroleum coke;
the mixed acid is mixed liquid of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 1:0.7;
s2, preparing polydopamine modified carbon fibers: adding 10g of carbon fiber into 200mL of water, adding 2g of dopamine hydrochloride and 0.1g of catalyst, heating to 40 ℃, stirring for reaction for 2h, centrifuging, washing and drying to obtain polydopamine modified carbon fiber;
The catalyst is Tris-HCl solution with pH=8.5;
s3, preparing an asphalt binder: adding 3g of polydopamine modified carbon fiber into 10g of asphalt, and stirring and mixing for 20min to prepare an asphalt binder;
S4, pressing: uniformly mixing 10g of puffed petroleum coke and 2g of asphalt binder, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of 80 tons by a press roller to obtain compacted petroleum coke;
S5, calcining: heating the compacted and calcined petroleum coke to 1100 ℃, and calcining for 1h to obtain the compacted and calcined petroleum coke.
Example 2
The embodiment provides a production method of compacted and calcined petroleum coke, which specifically comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10g of petroleum coke, mixing with 2g of CaO, ball milling, adding 70mL of 12wt% hydrogen peroxide, heating to 50 ℃, stirring for reaction for 40min, filtering, adding 50mL of mixed acid, stirring for reaction for 50min, filtering, washing, drying, puffing at 250 ℃ for 3h, and obtaining puffed petroleum coke;
The mixed acid is mixed liquid of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 1:1.2;
S2, preparing polydopamine modified carbon fibers: adding 10g of carbon fiber into 200mL of water, adding 3g of dopamine hydrochloride and 0.2g of catalyst, heating to 50 ℃, stirring for reaction for 3h, centrifuging, washing and drying to obtain polydopamine modified carbon fiber;
the catalyst is Tris-HCl solution with pH=9.5;
s3, preparing an asphalt binder: adding 5g of polydopamine modified carbon fiber into 10g of asphalt, and stirring and mixing for 40min to prepare an asphalt binder;
s4, pressing: uniformly mixing 10g of puffed petroleum coke and 3g of asphalt binder, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of a press roll of 100 tons to obtain compacted petroleum coke;
S5, calcining: heating the compacted and calcined petroleum coke to 1300 ℃, and calcining for 3 hours to obtain the compacted and calcined petroleum coke.
Example 3
The embodiment provides a production method of compacted and calcined petroleum coke, which specifically comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10g of petroleum coke, mixing with 1.5g of CaO, ball milling, adding 60mL of 10wt% hydrogen peroxide, heating to 45 ℃, stirring and reacting for 35min, filtering, adding 40mL of mixed acid, stirring and reacting for 40min, filtering, washing, drying, puffing at 200 ℃ for 2h, and obtaining puffed petroleum coke;
The mixed acid is mixed liquid of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 1:1;
s2, preparing polydopamine modified carbon fibers: adding 10g of carbon fiber into 200mL of water, adding 2.5g of dopamine hydrochloride and 0.15g of catalyst, heating to 45 ℃, stirring and reacting for 2.5h, centrifuging, washing and drying to obtain polydopamine modified carbon fiber;
The catalyst is Tris-HCl solution with pH=9;
s3, preparing an asphalt binder: adding 4g of polydopamine modified carbon fiber into 10g of asphalt, and stirring and mixing for 30min to prepare an asphalt binder;
S4, pressing: uniformly mixing 10g of puffed petroleum coke and 2.5g of asphalt binder, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of 90 tons by a press roller to obtain compacted petroleum coke;
s5, calcining: heating the compacted and calcined petroleum coke to 1200 ℃ and calcining for 2 hours to obtain the compacted and calcined petroleum coke.
Comparative example 1
In contrast to example 3, the difference is that the hydrogen peroxide treatment is not performed in step S1.
The method comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10g of petroleum coke, mixing with 1.5g of CaO, ball milling, adding into 40mL of mixed acid, stirring for reacting for 40min, filtering, washing, drying, puffing at 200 ℃ for 2h, and obtaining puffed petroleum coke;
The mixed acid is mixed liquid of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 1:1;
s2, preparing polydopamine modified carbon fibers: adding 10g of carbon fiber into 200mL of water, adding 2.5g of dopamine hydrochloride and 0.15g of catalyst, heating to 45 ℃, stirring and reacting for 2.5h, centrifuging, washing and drying to obtain polydopamine modified carbon fiber;
The catalyst is Tris-HCl solution with pH=9;
s3, preparing an asphalt binder: adding 4g of polydopamine modified carbon fiber into 10g of asphalt, and stirring and mixing for 30min to prepare an asphalt binder;
S4, pressing: uniformly mixing 10g of puffed petroleum coke and 2.5g of asphalt binder, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of 90 tons by a press roller to obtain compacted petroleum coke;
s5, calcining: heating the compacted and calcined petroleum coke to 1200 ℃ and calcining for 2 hours to obtain the compacted and calcined petroleum coke.
Comparative example 2
The difference compared to example 3 is that the mixed acid treatment is not performed in step S1.
The method comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10g of petroleum coke, mixing with 1.5g of CaO, ball milling, adding 60mL of 10wt% hydrogen peroxide, heating to 45 ℃, stirring for reaction for 35min, filtering, washing, drying, puffing at 200 ℃ for 2h, and obtaining puffed petroleum coke;
s2, preparing polydopamine modified carbon fibers: adding 10g of carbon fiber into 200mL of water, adding 2.5g of dopamine hydrochloride and 0.15g of catalyst, heating to 45 ℃, stirring and reacting for 2.5h, centrifuging, washing and drying to obtain polydopamine modified carbon fiber;
The catalyst is Tris-HCl solution with pH=9;
s3, preparing an asphalt binder: adding 4g of polydopamine modified carbon fiber into 10g of asphalt, and stirring and mixing for 30min to prepare an asphalt binder;
S4, pressing: uniformly mixing 10g of puffed petroleum coke and 2.5g of asphalt binder, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of 90 tons by a press roller to obtain compacted petroleum coke;
s5, calcining: heating the compacted and calcined petroleum coke to 1200 ℃ and calcining for 2 hours to obtain the compacted and calcined petroleum coke.
Comparative example 3
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10g of petroleum coke, mixing with 1.5g of CaO, ball milling, adding 60mL of 10wt% hydrogen peroxide, heating to 45 ℃, stirring and reacting for 35min, filtering, adding 40mL of mixed acid, stirring and reacting for 40min, filtering, washing, drying, puffing at 200 ℃ for 2h, and obtaining puffed petroleum coke;
The mixed acid is mixed liquid of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 1:1;
S2, preparing an asphalt binder: adding 4g of carbon fiber into 10g of asphalt, and stirring and mixing for 30min to prepare an asphalt binder;
S3, pressing: uniformly mixing 10g of puffed petroleum coke and 2.5g of asphalt binder, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of 90 tons by a press roller to obtain compacted petroleum coke;
S4, calcining: heating the compacted and calcined petroleum coke to 1200 ℃ and calcining for 2 hours to obtain the compacted and calcined petroleum coke.
Comparative example 4
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
S1, preparing puffed petroleum coke: crushing 10g of petroleum coke, mixing with 1.5g of CaO, ball milling, adding 60mL of 10wt% hydrogen peroxide, heating to 45 ℃, stirring and reacting for 35min, filtering, adding 40mL of mixed acid, stirring and reacting for 40min, filtering, washing, drying, puffing at 200 ℃ for 2h, and obtaining puffed petroleum coke;
The mixed acid is mixed liquid of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 1:1;
s2, preparing polydopamine modified carbon fibers: adding 10g of carbon fiber into 200mL of water, adding 2.5g of dopamine hydrochloride and 0.15g of catalyst, heating to 45 ℃, stirring and reacting for 2.5h, centrifuging, washing and drying to obtain polydopamine modified carbon fiber;
The catalyst is Tris-HCl solution with pH=9;
S3, pressing: uniformly mixing 10g of puffed petroleum coke with 2.5g of asphalt, feeding the mixture into a ball press, and pressing the mixture into blocks with a hydraulic thrust of 90 tons by a press roller to obtain compacted petroleum coke;
S4, calcining: heating the compacted and calcined petroleum coke to 1200 ℃ and calcining for 2 hours to obtain the compacted and calcined petroleum coke.
Test example 1 desulfurization rate
The residual sulfur mass fraction of the compacted calcined petroleum coke obtained in examples 1 to 3 and comparative examples 1 to 4 was measured using a microcomputer coulometric sulfur analyzer (CLS-3000), and the final desulfurization rate (%) of the petroleum coke was calculated as follows. The results are shown in Table 1.
Desulfurization rate (%) = (w 0-w1）/w0 ×100%
Wherein: w 0 and w 1 represent the sulfur mass fraction of the petroleum coke and the residual sulfur mass fraction of the compacted calcined petroleum coke, respectively.
TABLE 1
；
As shown in the table above, the pressed and calcined petroleum coke prepared in examples 1-3 of the present invention has a good desulfurization rate.
Test example 2
According to the standard: YS-T625-2012 the powder resistivity of compacted calcined petroleum coke produced in examples 1-3 and comparative examples 1-4 was measured and the results are shown in Table 2.
TABLE 2
；
As can be seen from the above table, the compacted calcined petroleum coke prepared in examples 1-3 of the present invention has a lower powder resistivity.
Test example 3
The pressed calcined petroleum coke prepared in examples 1-3 and comparative examples 1-4 of the present invention was subjected to performance testing.
Apparent porosity: the detection is carried out according to the method of GB/T4511.1-2008.
True specific gravity: the detection is carried out according to the method of GB/T4511.4-84.
Flexural resistance: the flexural strength of the material was tested by a three-point bending method using a universal tester, with a specimen format of 5X 10X 50 mm 3 bar samples. The calculation formula is as follows:
；
Wherein: Flexural strength, MPa; p is the maximum bending resistance, N; l is the test span, 40 mm; b is the width of the sample, mm; h is the thickness of the sample, mm.
The results are shown in Table 3.
TABLE 3 Table 3
；
As can be seen from the above table, the pressed and calcined petroleum coke prepared in examples 1 to 3 of the present invention has a higher density and a higher porosity.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The production method of the compacted calcined petroleum coke is characterized by comprising the following steps of:
S1, preparing puffed petroleum coke: crushing petroleum coke, mixing with CaO, ball milling, adding the crushed petroleum coke into hydrogen peroxide, heating, stirring, reacting, filtering, adding the mixed acid into the mixed acid, stirring, reacting, filtering, washing, drying, and puffing at a low temperature to obtain puffed petroleum coke, wherein the mixed acid is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, the volume ratio is 1:0.7-1.2, the temperature of the low temperature puffing treatment is 150-250 ℃, the time is 1-3h, and the mass ratio of the petroleum coke to the CaO is 10:1-2;
S2, preparing polydopamine modified carbon fibers: adding carbon fiber into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, centrifuging, washing, and drying to obtain polydopamine modified carbon fiber, wherein the mass ratio of the carbon fiber to the dopamine hydrochloride to the catalyst is 10:2-3:0.1-0.2;
S3, preparing an asphalt binder: adding polydopamine modified carbon fiber into asphalt, and uniformly stirring and mixing to obtain an asphalt binder, wherein the mass ratio of polydopamine modified carbon fiber to asphalt is 3-5:10;
s4, pressing: uniformly mixing the puffed petroleum coke and the asphalt binder, and pressing the mixture into blocks by a ball pressing machine to obtain pressed petroleum coke, wherein the mass ratio of the puffed petroleum coke to the asphalt binder is 10:2-3;
S5, calcining: calcining the compacted petroleum coke to obtain the compacted and calcined petroleum coke.
2. The method according to claim 1, wherein the temperature of the heating and stirring reaction in step S1 is 40-50 ℃ for 30-40min, and the stirring reaction time is 30-50min.
3. The production method according to claim 1, wherein in the step S1, the solid-to-liquid ratio of petroleum coke and hydrogen peroxide is 1g:5-7mL, and the solid-to-liquid ratio of petroleum coke and mixed acid is 1g:3-5mL, wherein the concentration of the hydrogen peroxide is 8-12wt%.
4. The method according to claim 1, wherein the catalyst in step S2 is Tris-HCl solution having ph=8.5-9.5, and the temperature of the heating and stirring reaction is 40-50 ℃ for 2-3 hours.
5. The method according to claim 1, wherein the stirring and mixing time in step S3 is 20 to 40 minutes.
6. The production method according to claim 1, wherein the hydraulic thrust of the press roll of the ball press machine in step S4 is 80-100 tons.
7. The method according to claim 1, wherein the calcination in step S5 is performed at a temperature of 1100 to 1300 ℃ for a time of1 to 3 hours.
8. A compacted calcined petroleum coke produced by the production process of any one of claims 1 to 7.
9. Use of compacted calcined petroleum coke according to claim 8 for the preparation of carbon products.
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