CN107128914A - The preparation method of petroleum coke pilum shaped activated carbon - Google Patents
The preparation method of petroleum coke pilum shaped activated carbon Download PDFInfo
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- CN107128914A CN107128914A CN201710538010.4A CN201710538010A CN107128914A CN 107128914 A CN107128914 A CN 107128914A CN 201710538010 A CN201710538010 A CN 201710538010A CN 107128914 A CN107128914 A CN 107128914A
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- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The invention discloses a kind of preparation method of petroleum coke pilum shaped activated carbon, this method uses pitch for matrix, in the case where being further condensed with phenolic aldehyde, it is 290~350 DEG C, the carbonaceous binder of carbon residue 72%~82% to form softening point, and with additional adhesive collective effect, with petroleum coke powder through kneading, shaping, charing and activation, intensity is prepared into up to 86%~95%, 690~1000mg/g of iodine sorption value, the high-quality petroleum coke pilum shaped activated carbon of ash content 0.2%~0.35%.Present invention, avoiding using the pollution to equipment and environment caused by analysis for preparation of activated carbon by chemical activation, it also avoid the problems such as combination property is poor in prepared by pressed active carbon, available for preparing high-quality petroleum coke pilum shaped activated carbon.
Description
Technical field
The invention belongs to the preparing technical field of activated carbon, more particularly to a kind of preparation of petroleum coke pilum shaped activated carbon
Method.
Background technology
Petroleum coke is a kind of byproduct in oil plant oil refining process, and its yield is about the 25%~30% of feedstock oil, carbon
Content and calorific value are very high, and ash content and volatile matter are very low.With oil demand the development being continuously increased with crude oil deep processing and
The heaviness of world's crude oil, the yield of petroleum coke is continuously increased.Therefore, the rational and efficient use of petroleum coke turns into growing interest
Problem.At present, sulfur content is relatively low and the preferable petroleum coke of quality is mainly used in several big industries such as cement and metallurgy, but with me
The substantial increase of state's imported crude oil, Petrol Coke In Refining Factory sulfur content is greatly increased, it is difficult to the high-quality such as graphite electrode, anode mix are made
Carbon product, mostly as the fuel of low value, producing activated carbon with it has larger development potentiality.
Research of the countries in the world for producing activated carbon by raw material of petroleum coke mostly concentrates on chemical method, though the technique energy
Be made active carbon with high specific surface area, but exist process route length, cost it is high, it is serious to equipment corrosion the shortcomings of.For vapor
Activation method prepares petroleum coke pilum shaped activated carbon, and due to petroleum coke close structure, crystallinity is high.Using general active carbon from coal
With binding agent, such as coal tar pitch, coal tar or some auxiliary elements, activated carbon low intensity, specific surface area is small.Using petroleum coke powder as
The conventional method that raw material makes activated carbon is that it adds additional adhesive (such as carboxymethyl cellulose, Sodium Alginate, gelatine, poly- second
Enol etc.), by extrusion molding after kneading, after carbonization-activation maximum intensity be 62%, 320~400mg/g of iodine sorption value,
Ash content 0.2%~0.4%.Also there is the report using doping high temperature resistant bonding agent, although intensity and increased than surface, but draw
A large amount of ash contents and impurity, influence product final performance and application are entered.
The content of the invention
The technical problems to be solved by the invention, which are to overcome in above-mentioned petroleum coke pilum shaped activated carbon preparation process, to be present
The problem of prepare that intensity is high, specific surface area is big, content of ashes is low there is provided a kind of carbonaceous binder of high carbon residue of utilization high softening-point
Petroleum coke pilum shaped activated carbon method.
The scheme that solution above-mentioned technical problem is used is made up of following step：
1st, compressive reaction
It is 1 in mass ratio by pitch and phenolic compound, aldehyde compound, acid:(0.01~0.2):(0.1~0.3):
(0.01~0.09) add in reactor, be heated to 50~90 DEG C under stirring, isothermal reaction 1~7 hour, pressure is constant
In 0.1~5Mpa.
Above-mentioned pitch is petroleum residual oil, de-oiled asphalt, coal tar, coalite tar, medium temperature coal tar, high temperature coal-tar
In any one or two or more mixtures, phenolic compound is any one in phenol, hydroquinones, resorcinol
Kind, the paraformaldehyde that aldehyde compound is formaldehyde or the degree of polymerization is 8~100, acid is oxalic acid, acetic acid, citric acid, maleic acid, second
Any one in diacid.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 350~450 DEG C in a kettle., in 0~-0.096MPa
Lower isothermal reaction 10~60 minutes, is prepared into carbonaceous binder.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, according to petroleum coke powder, carbon
Matter bonding agent, additional adhesive, the mass ratio of water are 100:(10~80):(5~30):(5~30) kneading is uniform, using extrusion
Method of forming extrusion molding, dries.
Above-mentioned additional adhesive is any one in carboxymethyl cellulose, Sodium Alginate, gelatine, polyvinyl alcohol.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, heated up with 1~5 DEG C/min of heating rate
Vapor, priming reaction 60~150 minutes, reaction knot are passed through to 700~900 DEG C, and by 0.2~0.6mL/min.g flow velocity
Taken out after Shu Hou, Temperature fall, produce petroleum coke pilum shaped activated carbon.
In above-mentioned steps 1, preferably pitch and phenolic compound, aldehyde compound, acid are 1 in mass ratio:(0.10~
0.15):(0.1~0.2):(0.04~0.05).
In above-mentioned steps 1,60~75 DEG C, isothermal reaction 3~5 hours, pressure are further preferably heated under stirring
Power is constant in 3~4MPa.
In above-mentioned steps 2, preferably the product after step 1 compressive reaction is continued to be warming up to 390~410 in a kettle.
DEG C, isothermal reaction 25~50 minutes under -0.05~-0.07MPa.
In above-mentioned steps 3, preferably petroleum coke powder, carbonaceous binder, additional adhesive, the mass ratio of water are 100:(30~
50):(5~20):(10~20).
In above-mentioned steps 4, preferably in N2Under protection, 780~850 DEG C are warming up to 3~4 DEG C/min of heating rate, and
Vapor, priming reaction 80~120 minutes are passed through by 0.4~0.5mL/min.g flow velocity.
The present invention uses pitch for matrix, in the case where being further condensed with phenolic aldehyde, forms softening point for 290~350 DEG C, carbon residue
72%~82% carbonaceous binder, and with additional adhesive collective effect, with petroleum coke powder through kneading, shaping, charing and living
Change, be prepared into intensity up to 86%~95%, 690~1000mg/g of iodine sorption value, the high-quality petroleum coke of ash content 0.2%~0.35%
Pilum shaped activated carbon.Present invention, avoiding the pollution to equipment and environment caused by use analysis for preparation of activated carbon by chemical activation,
The problems such as combination property is poor in prepared by pressed active carbon is it also avoid, available for preparing high-quality petroleum coke pilum shaped activated carbon.
Embodiment
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Activated carbon intensity uses intensity in GB/T7702.3-2008 ature of coal granular activated carbon test methods in example below
Assay method, according to GBT12496.8-1999《The measure of wood activated charcoal test method iodine sorption value》Determine iodine sorption value,
According to GBT 603-2002《The preparation of preparation and product used in chemical reagent test method》Standard liquid needed for preparing, and mark
It is fixed.
Embodiment 1
1st, compressive reaction
100g de-oiled asphalts, 10g hydroquinones, 20g formaldehyde, 5g citric acids are added in reactor, and open magnetic force and is stirred
Device is mixed, regulation pressure is 2MPa when being warming up to 80 DEG C, is kept for 4 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 370 DEG C in a kettle., regulation pressure is -0.07MPa,
Isothermal reaction 30 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 253 DEG C, carbon residue is 67.8%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
120g carbonaceous binders, 30g carboxymethyl celluloses, 60g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion
Method of forming extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
800 DEG C, and vapor is passed through by 0.5mL/min.g flow velocity, priming reaction 100 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 84%, iodine sorption value 672mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.385%.
Embodiment 2
1st, compressive reaction
100g petroleum residual oils, 10g resorcinols, 20g formaldehyde, 8g acetic acid are added in reactor, and opens magnetic agitation
Device, regulation pressure is 4MPa when being warming up to 65 DEG C, is kept for 3 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 380 DEG C in a kettle., regulation pressure is -0.08MPa,
Isothermal reaction 25 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 273 DEG C, carbon residue is 69.4%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
120g carbonaceous binders, 60g carboxymethyl celluloses, 60g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion
Method of forming extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
780 DEG C, and vapor is passed through by 0.4mL/min.g flow velocity, priming reaction 120 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 87%, iodine sorption value 697mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.369%.
Embodiment 3
1st, compressive reaction
100g de-oiled asphalts, 5g phenol, the paraformaldehyde that the 10g degree of polymerization is 8,3g acetic acid are added in reactor, and opened
Magnetic stirring apparatus is opened, regulation pressure is 3MPa when being warming up to 65 DEG C, is kept for 2 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 380 DEG C in a kettle., regulation pressure is -0.03MPa,
Isothermal reaction 25 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 225 DEG C, carbon residue is 64.2%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
90g carbonaceous binders, 60g carboxymethyl celluloses, 60g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion into
Type method extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
750 DEG C, and vapor is passed through by 0.3mL/min.g flow velocity, priming reaction 130 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 80%, iodine sorption value 600mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.5%.
Embodiment 4
1st, compressive reaction
100g high temperature coal-tars, 15g hydroquinones, 20g formaldehyde, 5g oxalic acid are added in reactor, and open magnetic force and is stirred
Device is mixed, regulation pressure is 3MPa when being warming up to 60 DEG C, is kept for 3 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 390 DEG C in a kettle., regulation pressure is -0.05MPa,
Isothermal reaction 40 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 302 DEG C, carbon residue is 73.7%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
120g carbonaceous binders, 30g carboxymethyl celluloses, 60g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion
Method of forming extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
810 DEG C, and vapor is passed through by 0.5mL/min.g flow velocity, priming reaction 100 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 89%, iodine sorption value 838mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.296%.
Embodiment 5
1st, compressive reaction
100g petroleum residual oils, 15g phenol, the paraformaldehyde that the 15g degree of polymerization is 100,5g acetic acid are added in reactor, and
Magnetic stirring apparatus is opened, regulation pressure is 3MPa when being warming up to 70 DEG C, is kept for 4 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 390 DEG C in a kettle., regulation pressure is -0.05MPa,
Isothermal reaction 50 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 308 DEG C, carbon residue is 74.5%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 200g coke powders,
100g carbonaceous binders, 20g carboxymethyl celluloses, 40g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion
Method of forming extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
820 DEG C, and vapor is passed through by 0.4mL/min.g flow velocity, priming reaction 120 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 90%, iodine sorption value 840mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.302%.
Embodiment 6
1st, compressive reaction
100g de-oiled asphalts, 10g phenol, 20g formaldehyde, 5g acetic acid are added in reactor, and opens magnetic stirring apparatus, is risen
Temperature is 3MPa to pressure is adjusted at 70 DEG C, is kept for 3 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle., regulation pressure is -0.06MPa,
Isothermal reaction 35 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 335 DEG C, carbon residue is 80.4%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
120g carbonaceous binders, 30g carboxymethyl celluloses, 60g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion
Method of forming extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
800 DEG C, and vapor is passed through by 0.5mL/min.g flow velocity, priming reaction 120 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 95%, iodine sorption value 1000mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.2%.
Embodiment 7
1st, compressive reaction
100g medium temperature coal tars, 10g resorcinols, 20g formaldehyde, 4g oxalic acid are added in reactor, and open magnetic force and is stirred
Device is mixed, regulation pressure is 3MPa when being warming up to 75 DEG C, is kept for 3 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle., regulation pressure is -0.06MPa,
Isothermal reaction 30 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 324 DEG C, carbon residue is 78.5%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
120g carbonaceous binders, 60g Sodium Alginates, 60g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extruded moulding
Method extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 4 DEG C/min of heating rate
800 DEG C, and vapor is passed through by 0.6mL/min.g flow velocity, priming reaction 120 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 93%, iodine sorption value 918mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.277%.
Embodiment 8
1st, compressive reaction
100g de-oiled asphalts, 10g phenol, 15g formaldehyde, 5g maleic acids are added in reactor, and open magnetic stirring apparatus,
Regulation pressure is 3MPa when being warming up to 70 DEG C, is kept for 3 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle., regulation pressure is -0.03MPa,
Isothermal reaction 25 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 295 DEG C, carbon residue is 71.9%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
90g carbonaceous binders, 15g gelatine, 30g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extruded moulding method extrusion
Shaping, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 4 DEG C/min of heating rate
850 DEG C, and vapor is passed through by 0.5mL/min.g flow velocity, priming reaction 80 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 86%, iodine sorption value 786mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.307%.
Embodiment 9
1st, compressive reaction
Paraformaldehyde, 5g ethanedioic acids addition reactor by 100g petroleum residual oils, 15g hydroquinones, the 10g degree of polymerization for 8
In, and magnetic stirring apparatus is opened, regulation pressure is 4MPa when being warming up to 70 DEG C, is kept for 4 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle., regulation pressure is -0.07MPa,
Isothermal reaction 30 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 346 DEG C, carbon residue is 82.2%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
120g carbonaceous binders, 30g carboxymethyl celluloses, 30g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion
Method of forming extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
800 DEG C, and vapor is passed through by 0.5mL/min.g flow velocity, priming reaction 90 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 92%, iodine sorption value 879mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.238%.
Embodiment 10
1st, compressive reaction
100g petroleum residual oils, 10g phenol, the paraformaldehyde that the 20g degree of polymerization is 100,5g acetic acid are added in reactor, and
Magnetic stirring apparatus is opened, regulation pressure is 3MPa when being warming up to 75 DEG C, is kept for 5 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 410 DEG C in a kettle., regulation pressure is -0.055MPa,
Isothermal reaction 25 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 292 DEG C, carbon residue is 72.3%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 200g coke powders,
100g carbonaceous binders, 40g polyvinyl alcohol (degree of polymerization 1750), 20g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then
Using extruded moulding method extrusion molding, dry.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 4 DEG C/min of heating rate
780 DEG C, and vapor is passed through by 0.4mL/min.g flow velocity, priming reaction 110 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 91%, iodine sorption value 804mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.336%.
Embodiment 11
1st, compressive reaction
100g de-oiled asphalts, 5g phenol, 10g formaldehyde, 6g citric acids are added in reactor, and open magnetic stirring apparatus,
Regulation pressure is 1MPa when being warming up to 70 DEG C, is kept for 4 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 410 DEG C in a kettle., regulation pressure is -0.05MPa,
Isothermal reaction 30 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 278 DEG C, carbon residue is 70.2%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 300g coke powders,
60g carbonaceous binders, 30g carboxymethyl celluloses, 30g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion into
Type method extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 3 DEG C/min of heating rate
810 DEG C, and vapor is passed through by 0.5mL/min.g flow velocity, priming reaction 120 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 86%, iodine sorption value 689mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.368%.
Embodiment 12
1st, compressive reaction
100g high temperature coal-tars, 10g resorcinols, 30g formaldehyde, 5g maleic acids are added in reactor, and open magnetic force
Agitator, regulation pressure is 3MPa when being warming up to 70 DEG C, is kept for 3 hours, pressure then is adjusted into 0MPa.
2nd, polycondensation reaction is depressurized
Product after step 1 compressive reaction is continuously heating to 430 DEG C in a kettle., regulation pressure is -0.045MPa,
Isothermal reaction 20 minutes, reaction discharges after terminating, and obtains the carbonaceous binder that softening point is 248 DEG C, carbon residue is 73.3%.
3rd, it is molded
Petroleum coke and step 2 gained carbonaceous binder are crushed levigate to below 200 mesh respectively, then by 200g coke powders,
120g carbonaceous binders, 20g carboxymethyl celluloses, 30g water are fitted into kneading extrusion all-in-one, and kneading is uniform, then using extrusion
Method of forming extrusion molding, dries.
4th, petroleum coke pilum shaped activated carbon is prepared
Step 3 gained column type carbon is placed in tube furnace, in N2Under protection, it is warming up to 2 DEG C/min of heating rate
800 DEG C, and vapor is passed through by 0.5mL/min.g flow velocity, priming reaction 100 minutes after reaction terminates, takes after Temperature fall
Go out, that is, obtain intensity 82%, iodine sorption value 657mg/g, the petroleum coke pilum shaped activated carbon of ash content 0.412%.
Claims (6)
1. a kind of preparation method of petroleum coke pilum shaped activated carbon, it is characterised in that it is made up of following step：
(1) compressive reaction
It is 1 in mass ratio by pitch and phenolic compound, aldehyde compound, acid:(0.01~0.2):(0.1~0.3):(0.01
~0.09) add in reactor, it is heated to 50~90 DEG C under stirring, isothermal reaction 1~7 hour, pressure is constant 0.1
~5MPa；
Above-mentioned pitch is in petroleum residual oil, de-oiled asphalt, coal tar, coalite tar, medium temperature coal tar, high temperature coal-tar
Any one or two or more mixtures, phenolic compound are any one in phenol, hydroquinones, resorcinol, aldehyde
The paraformaldehyde that class compound is formaldehyde or the degree of polymerization is 8~100, acid is in oxalic acid, acetic acid, citric acid, maleic acid, ethanedioic acid
Any one；
(2) polycondensation reaction is depressurized
Product after step (1) compressive reaction is continuously heating to 350~450 DEG C in a kettle., under 0~-0.096MPa
Isothermal reaction 10~60 minutes, is prepared into carbonaceous binder；
(3) it is molded
Carbonaceous binder obtained by petroleum coke and step (2) is crushed levigate to below 200 mesh respectively, according to petroleum coke powder, carbonaceous
Bonding agent, additional adhesive, the mass ratio of water are 100:(10~80):(5~30):(5~30) kneading is uniform, using extrusion into
Type method extrusion molding, dries；
Above-mentioned additional adhesive is any one in carboxymethyl cellulose, Sodium Alginate, gelatine, polyvinyl alcohol；
(4) petroleum coke pilum shaped activated carbon is prepared
Column type carbon obtained by step (3) is placed in tube furnace, in N2Under protection, it is warming up to 1~5 DEG C/min of heating rate
700~900 DEG C, and it is passed through vapor by 0.2~0.6mL/min.g flow velocity, priming reaction 60~150 minutes, reaction terminates
Afterwards, taken out after Temperature fall, produce petroleum coke pilum shaped activated carbon.
2. the preparation method of petroleum coke pilum shaped activated carbon according to claim 1, it is characterised in that：In step (1), institute
It is 1 in mass ratio that pitch, which is stated, with phenolic compound, aldehyde compound, acid:(0.10~0.15):(0.1~0.2):(0.04~
0.05)。
3. the preparation method of petroleum coke pilum shaped activated carbon according to claim 1, it is characterised in that：In step (1),
It is heated to 60~75 DEG C under stirring, isothermal reaction 3~5 hours, pressure is constant in 3~4MPa.
4. the preparation method of petroleum coke pilum shaped activated carbon according to claim 1, it is characterised in that：, will in step (2)
Product after step (1) compressive reaction continues to be warming up to 390~410 DEG C in a kettle., the constant temperature under -0.05~-0.07MPa
Reaction 25~50 minutes.
5. the preparation method of petroleum coke pilum shaped activated carbon according to claim 1, it is characterised in that：In step (3), institute
It is 100 to state petroleum coke powder, carbonaceous binder, additional adhesive, the mass ratio of water:(30~50):(5~20):(10~20).
6. the preparation method of petroleum coke pilum shaped activated carbon according to claim 1, it is characterised in that：In step (4),
N2Under protection, 780~850 DEG C are warming up to 3~4 DEG C/min of heating rate, and lead to by 0.4~0.5mL/min.g flow velocity
Enter vapor, priming reaction 80~120 minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751193A (en) * | 2018-08-29 | 2018-11-06 | 陕西师范大学 | A kind of preparation method of semi-coke end pilum shaped activated carbon |
| CN109467085A (en) * | 2018-12-27 | 2019-03-15 | 中国铝业股份有限公司 | A kind of preparation method of ultralow ash content active carbon |
| CN110817868A (en) * | 2019-12-13 | 2020-02-21 | 陕西师范大学 | Preparation method of high-strength mesoporous carbon |
| CN112678820A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of columnar sulfur-carrying activated carbon |
| CN114084936A (en) * | 2021-11-24 | 2022-02-25 | 南京信息工程大学 | Carbon material for degrading sulfonamide antibiotics based on electro-Fenton reaction and preparation method thereof |
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| CN102791628A (en) * | 2010-02-19 | 2012-11-21 | 创业发展联盟技术有限公司 | Carbon material and method for producing same |
| CN107935614A (en) * | 2017-11-30 | 2018-04-20 | 北京天宜上佳新材料股份有限公司 | Carbon ceramic composite material and preparation method thereof |
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| CN102791628A (en) * | 2010-02-19 | 2012-11-21 | 创业发展联盟技术有限公司 | Carbon material and method for producing same |
| CN107935614A (en) * | 2017-11-30 | 2018-04-20 | 北京天宜上佳新材料股份有限公司 | Carbon ceramic composite material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751193A (en) * | 2018-08-29 | 2018-11-06 | 陕西师范大学 | A kind of preparation method of semi-coke end pilum shaped activated carbon |
| CN109467085A (en) * | 2018-12-27 | 2019-03-15 | 中国铝业股份有限公司 | A kind of preparation method of ultralow ash content active carbon |
| CN112678820A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of columnar sulfur-carrying activated carbon |
| CN110817868A (en) * | 2019-12-13 | 2020-02-21 | 陕西师范大学 | Preparation method of high-strength mesoporous carbon |
| CN114084936A (en) * | 2021-11-24 | 2022-02-25 | 南京信息工程大学 | Carbon material for degrading sulfonamide antibiotics based on electro-Fenton reaction and preparation method thereof |
| CN114084936B (en) * | 2021-11-24 | 2023-10-27 | 南京信息工程大学 | Carbon material for degrading sulfonamide antibiotics based on electro-Fenton reaction and preparation method thereof |
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