CN107128914B - Preparation method of petroleum coke-based columnar activated carbon - Google Patents
Preparation method of petroleum coke-based columnar activated carbon Download PDFInfo
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- CN107128914B CN107128914B CN201710538010.4A CN201710538010A CN107128914B CN 107128914 B CN107128914 B CN 107128914B CN 201710538010 A CN201710538010 A CN 201710538010A CN 107128914 B CN107128914 B CN 107128914B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000002006 petroleum coke Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011233 carbonaceous binding agent Substances 0.000 claims abstract description 45
- 238000004898 kneading Methods 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 106
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000010792 warming Methods 0.000 claims description 28
- 238000001125 extrusion Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 18
- 230000037452 priming Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- 238000006482 condensation reaction Methods 0.000 claims description 14
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011280 coal tar Substances 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010426 asphalt Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001828 Gelatine Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011269 tar Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052740 iodine Inorganic materials 0.000 abstract description 17
- 239000011630 iodine Substances 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 238000000465 moulding Methods 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002956 ash Substances 0.000 description 17
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000011295 pitch Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of petroleum coke pilum shaped activated carbon, this method uses pitch for matrix, in the case where being further condensed with phenolic aldehyde, form the carbonaceous binder that softening point is 290~350 DEG C, carbon residue 72%~82%, and with additional adhesive collective effect, with petroleum coke powder through kneading, molding, 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%.The invention avoids using the pollution caused by analysis for preparation of activated carbon by chemical activation to equipment and environment, the problems such as comprehensive performance is poor in pressed active carbon preparation is also avoided, can be used for preparing high-quality petroleum coke pilum shaped activated carbon.
Description
Technical field
The invention belongs to the preparation technical fields of active carbon, more particularly to a kind of preparation of petroleum coke pilum shaped activated carbon
Method.
Background technique
Petroleum coke is one of oil plant oil refining process byproduct, and 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 be continuously increased with the development of crude oil deep processing and
The yield of the heaviness of world's crude oil, petroleum coke is continuously increased.Therefore, petroleum coke is rationally and efficiently used as growing interest
Project.Currently, sulfur content is lower 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 greatly increase, it is difficult to it is high-quality that graphite electrode, anode mix etc. be made
Carbon product, mostly as the fuel of low value, producing active carbon with it has biggish development potentiality.
Countries in the world mostly concentrate on chemical method for the research for producing active carbon as raw material using petroleum coke, though the technique energy
Active carbon with high specific surface area is made, but the disadvantages of that there are process routes is long, at high cost, severe corrosion to equipment.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 binder, such as coal tar pitch, coal tar or some auxiliary elements, active carbon intensity is low, and specific surface area is small.It is with petroleum coke powder
The conventional method of raw material production active carbon is that additional adhesive (such as carboxymethyl cellulose, Sodium Alginate, gelatine, poly- second is added in it
Enol etc.), by extrusion molding after kneading, maximum intensity is 62%, 320~400mg/g of iodine sorption value after carbonization-activation,
Ash content 0.2%~0.4%.Also have and drawn using the report of doping high temperature resistant bonding agent although intensity and specific surface increase
Enter a large amount of ash contents and impurity, influences product final performance and application.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome in above-mentioned petroleum coke pilum shaped activated carbon preparation process to exist
The problem of, it provides a kind of low using carbonaceous binder preparation intensity height, large specific surface area, the content of ashes of the high carbon residue of high softening-point
Petroleum coke pilum shaped activated carbon method.
Scheme used by above-mentioned technical problem is solved to be made of following step:
1, compressive reaction
In mass ratio it is 1:(0.01~0.2 by pitch and phenolic compound, aldehyde compound, acid): (0.1~0.3):
(0.01~0.09) it is added in reaction kettle, 50~90 DEG C is heated under stirring, isothermal reaction 1~7 hour, pressure was 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 phenol, hydroquinone, any one in 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.
2, depressurization condensation reaction
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.
3, it forms
Petroleum coke and step 2 gained carbonaceous binder are crushed respectively levigate to 200 mesh hereinafter, according to petroleum coke powder, carbon
Matter bonding agent, additional adhesive, water mass ratio be 100:(10~80): (5~30): (5~30) kneading is uniform, using extrusion
Method of forming extrusion molding, dries.
Above-mentioned additional adhesive is carboxymethyl cellulose, Sodium Alginate, gelatine, any one in polyvinyl alcohol.
4, 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
It is passed through vapor to 700~900 DEG C, and by the flow velocity of 0.2~0.6mL/min, priming reaction 60~150 minutes, reaction terminated
Afterwards, it takes out after Temperature fall to get petroleum coke pilum shaped activated carbon.
In above-mentioned steps 1, preferably pitch and phenolic compound, aldehyde compound, acid in mass ratio for 1:(0.10~
0.15): (0.1~0.2): (0.04~0.05).
In above-mentioned steps 1, it is further preferably heated to 60~75 DEG C under stirring, isothermal reaction 3~5 hours, presses
Power is constant in 3~4MPa.
In above-mentioned steps 2, the product continuation after step 1 compressive reaction is preferably warming up to 390~410 in a kettle
DEG C, isothermal reaction 25~50 minutes at -0.05~-0.07MPa.
In above-mentioned steps 3, preferably petroleum coke powder, carbonaceous binder, additional adhesive, water mass ratio be 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 is passed through by the flow velocity of 0.4~0.5mL/min, priming reaction 80~120 minutes.
The present invention uses pitch for matrix, and in the case where being further condensed with phenolic aldehyde, forming softening point is 290~350 DEG C, carbon residue
72%~82% carbonaceous binder, and with additional adhesive collective effect, with petroleum coke powder through kneading, molding, charing and work
Change, is 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.The invention avoids using the pollution caused by analysis for preparation of activated carbon by chemical activation to equipment and environment,
The problems such as comprehensive performance is poor in pressed active carbon preparation is also avoided, can be used for preparing high-quality petroleum coke pilum shaped activated carbon.
Specific embodiment
Below 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.
Active carbon intensity is using intensity in GB/T7702.3-2008 coal quality granular activated carbon test method in following example
Measuring method, according to GBT12496.8-1999 " measurement of wood activated charcoal test method iodine sorption value " measure iodine sorption value,
Standard solution needed for being prepared according to the GBT 603-2002 preparation of preparation and product " in chemical reagent test method used ", and mark
It is fixed.
Embodiment 1
1, compressive reaction
100g de-oiled asphalt, 10g hydroquinone, 20g formaldehyde, 5g citric acid are added in reaction kettle, and open magnetic force and stir
Device is mixed, it is 2MPa that pressure is adjusted when being warming up to 80 DEG C, is kept for 4 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 370 DEG C in a kettle, adjusting pressure is -0.07MPa,
It isothermal reaction 30 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 253 DEG C, carbon residue is 67.8%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
120g carbonaceous binder, 30g carboxymethyl cellulose, 60g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extrusion
Method of forming extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.5mL/min, it priming reaction 100 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 84%, iodine sorption value 672mg/g, ash content 0.385% petroleum coke pilum shaped activated carbon.
Embodiment 2
1, compressive reaction
100g petroleum residual oil, 10g resorcinol, 20g formaldehyde, 8g acetic acid are added in reaction kettle, and open magnetic agitation
Device, it is 4MPa that pressure is adjusted when being warming up to 65 DEG C, is kept for 3 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 380 DEG C in a kettle, adjusting pressure is -0.08MPa,
It isothermal reaction 25 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 273 DEG C, carbon residue is 69.4%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
120g carbonaceous binder, 60g carboxymethyl cellulose, 60g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extrusion
Method of forming extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.4mL/min, it priming reaction 120 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 87%, iodine sorption value 697mg/g, ash content 0.369% petroleum coke pilum shaped activated carbon.
Embodiment 3
1, compressive reaction
100g de-oiled asphalt, 5g phenol, the paraformaldehyde that the 10g degree of polymerization is 8,3g acetic acid are added in reaction kettle, and opened
Magnetic stirring apparatus is opened, it is 3MPa that pressure is adjusted when being warming up to 65 DEG C, is kept for 2 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 380 DEG C in a kettle, adjusting pressure is -0.03MPa,
It isothermal reaction 25 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 225 DEG C, carbon residue is 64.2%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
90g carbonaceous binder, 60g carboxymethyl cellulose, 60g water be fitted into kneading squeeze out all-in-one machine in, kneading is uniform, then using extrusion at
Type method extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.3mL/min, it priming reaction 130 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 80%, iodine sorption value 600mg/g, ash content 0.5% petroleum coke pilum shaped activated carbon.
Embodiment 4
1, compressive reaction
100g high temperature coal-tar, 15g hydroquinone, 20g formaldehyde, 5g oxalic acid are added in reaction kettle, and open magnetic force and stir
Device is mixed, it is 3MPa that pressure is adjusted when being warming up to 60 DEG C, is kept for 3 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 390 DEG C in a kettle, adjusting pressure is -0.05MPa,
It isothermal reaction 40 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 302 DEG C, carbon residue is 73.7%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
120g carbonaceous binder, 30g carboxymethyl cellulose, 60g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extrusion
Method of forming extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.5mL/min, it priming reaction 100 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 89%, iodine sorption value 838mg/g, ash content 0.296% petroleum coke pilum shaped activated carbon.
Embodiment 5
1, compressive reaction
100g petroleum residual oil, 15g phenol, the paraformaldehyde that the 15g degree of polymerization is 100,5g acetic acid are added in reaction kettle, and
Magnetic stirring apparatus is opened, it is 3MPa that pressure is adjusted when being warming up to 70 DEG C, is kept for 4 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 390 DEG C in a kettle, adjusting pressure is -0.05MPa,
It isothermal reaction 50 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 308 DEG C, carbon residue is 74.5%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 200g coke powder,
100g carbonaceous binder, 20g carboxymethyl cellulose, 40g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extrusion
Method of forming extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.4mL/min, it priming reaction 120 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 90%, iodine sorption value 840mg/g, ash content 0.302% petroleum coke pilum shaped activated carbon.
Embodiment 6
1, compressive reaction
100g de-oiled asphalt, 10g phenol, 20g formaldehyde, 5g acetic acid are added in reaction kettle, and open magnetic stirring apparatus, is risen
It is 3MPa that pressure is adjusted when temperature is to 70 DEG C, is kept for 3 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle, adjusting pressure is -0.06MPa,
It isothermal reaction 35 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 335 DEG C, carbon residue is 80.4%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
120g carbonaceous binder, 30g carboxymethyl cellulose, 60g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extrusion
Method of forming extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.5mL/min, it priming reaction 120 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 95%, iodine sorption value 1000mg/g, ash content 0.2% petroleum coke pilum shaped activated carbon.
Embodiment 7
1, compressive reaction
100g medium temperature coal tar, 10g resorcinol, 20g formaldehyde, 4g oxalic acid are added in reaction kettle, and open magnetic force and stir
Device is mixed, it is 3MPa that pressure is adjusted when being warming up to 75 DEG C, is kept for 3 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle, adjusting pressure is -0.06MPa,
It isothermal reaction 30 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 324 DEG C, carbon residue is 78.5%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
120g carbonaceous binder, 60g Sodium Alginate, 60g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extruded moulding
Method extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.6mL/min, it priming reaction 120 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 93%, iodine sorption value 918mg/g, ash content 0.277% petroleum coke pilum shaped activated carbon.
Embodiment 8
1, compressive reaction
100g de-oiled asphalt, 10g phenol, 15g formaldehyde, 5g maleic acid are added in reaction kettle, and open magnetic stirring apparatus,
It is 3MPa that pressure is adjusted when being warming up to 70 DEG C, is kept for 3 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle, adjusting pressure is -0.03MPa,
It isothermal reaction 25 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 295 DEG C, carbon residue is 71.9%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
90g carbonaceous binder, 15g gelatine, 30g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then are squeezed out using extruded moulding method
Molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.5mL/min, it priming reaction 80 minutes, after reaction, is taken out after Temperature fall,
Obtain intensity 86%, iodine sorption value 786mg/g, ash content 0.307% petroleum coke pilum shaped activated carbon.
Embodiment 9
1, compressive reaction
Reaction kettle is added in 100g petroleum residual oil, 15g hydroquinone, the paraformaldehyde that the 10g degree of polymerization is 8,5g ethanedioic acid
In, and magnetic stirring apparatus is opened, it is 4MPa that pressure is adjusted when being warming up to 70 DEG C, is kept for 4 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 400 DEG C in a kettle, adjusting pressure is -0.07MPa,
It isothermal reaction 30 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 346 DEG C, carbon residue is 82.2%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
120g carbonaceous binder, 30g carboxymethyl cellulose, 30g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extrusion
Method of forming extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.5mL/min, it priming reaction 90 minutes, after reaction, is taken out after Temperature fall,
Obtain intensity 92%, iodine sorption value 879mg/g, ash content 0.238% petroleum coke pilum shaped activated carbon.
Embodiment 10
1, compressive reaction
100g petroleum residual oil, 10g phenol, the paraformaldehyde that the 20g degree of polymerization is 100,5g acetic acid are added in reaction kettle, and
Magnetic stirring apparatus is opened, it is 3MPa that pressure is adjusted when being warming up to 75 DEG C, is kept for 5 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 410 DEG C in a kettle, adjusting pressure is -0.055MPa,
It isothermal reaction 25 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 292 DEG C, carbon residue is 72.3%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 200g coke powder,
100g carbonaceous binder, 40g polyvinyl alcohol (degree of polymerization 1750), 20g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then
Using extruded moulding method extrusion molding, dry.
4, 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 it is passed through vapor by the flow velocity of 0.4mL/min, it priming reaction 110 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 91%, iodine sorption value 804mg/g, ash content 0.336% petroleum coke pilum shaped activated carbon.
Embodiment 11
1, compressive reaction
100g de-oiled asphalt, 5g phenol, 10g formaldehyde, 6g citric acid are added in reaction kettle, and open magnetic stirring apparatus,
It is 1MPa that pressure is adjusted when being warming up to 70 DEG C, is kept for 4 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 410 DEG C in a kettle, adjusting pressure is -0.05MPa,
It isothermal reaction 30 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 278 DEG C, carbon residue is 70.2%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 300g coke powder,
60g carbonaceous binder, 30g carboxymethyl cellulose, 30g water be fitted into kneading squeeze out all-in-one machine in, kneading is uniform, then using extrusion at
Type method extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.5mL/min, it priming reaction 120 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 86%, iodine sorption value 689mg/g, ash content 0.368% petroleum coke pilum shaped activated carbon.
Embodiment 12
1, compressive reaction
100g high temperature coal-tar, 10g resorcinol, 30g formaldehyde, 5g maleic acid are added in reaction kettle, and open magnetic force
Blender, it is 3MPa that pressure is adjusted when being warming up to 70 DEG C, is kept for 3 hours, pressure is then adjusted to 0MPa.
2, depressurization condensation reaction
Product after step 1 compressive reaction is continuously heating to 430 DEG C in a kettle, adjusting pressure is -0.045MPa,
It isothermal reaction 20 minutes, discharges after reaction, obtains the carbonaceous binder that softening point is 248 DEG C, carbon residue is 73.3%.
3, it forms
By petroleum coke and step 2 gained carbonaceous binder crush respectively it is levigate to 200 mesh hereinafter, then by 200g coke powder,
120g carbonaceous binder, 20g carboxymethyl cellulose, 30g water are fitted into kneading and squeeze out in all-in-one machine, and kneading is uniform, then use extrusion
Method of forming extrusion molding, dries.
4, 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 it is passed through vapor by the flow velocity of 0.5mL/min, it priming reaction 100 minutes, after reaction, is taken after Temperature fall
Out to get to intensity 82%, iodine sorption value 657mg/g, ash content 0.412% petroleum coke pilum shaped activated carbon.
Claims (6)
1. a kind of preparation method of petroleum coke pilum shaped activated carbon, it is characterised in that it is made of following step:
(1) compressive reaction
In mass ratio it is 1:(0.01~0.2 by pitch and phenolic compound, aldehyde compound, acid): (0.1~0.3): (0.01
~0.09) be added in reaction kettle, be heated to 50~90 DEG C under stirring, isothermal reaction 1~7 hour, pressure it is constant
0.1~5 MPa；
Above-mentioned pitch is petroleum residual oil, de-oiled asphalt, coalite tar, medium temperature coal tar, any one in high temperature coal-tar
Kind or two or more mixtures, phenolic compound be phenol, hydroquinone, any one in resorcinol, aldehydes chemical combination
The paraformaldehyde that object is formaldehyde or the degree of polymerization is 8~100, sour is any in oxalic acid, acetic acid, citric acid, maleic acid, ethanedioic acid
It is a kind of；
(2) depressurization condensation reaction
Product after step (1) compressive reaction is continuously heating to 350~450 DEG C in a kettle, in 0~-0.096 MPa
Lower isothermal reaction 10~60 minutes, is prepared into carbonaceous binder；
(3) it forms
Carbonaceous binder obtained by petroleum coke and step (2) is crushed respectively levigate to 200 mesh hereinafter, according to petroleum coke powder, carbonaceous
Bonding agent, additional adhesive, water mass ratio be 100:(10~80): (5~30): (5~30) kneading is uniform, using extrusion at
Type method extrusion molding, dries；
Above-mentioned additional adhesive is carboxymethyl cellulose, Sodium Alginate, gelatine, any one in 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 the flow velocity of 0.2~0.6 mL/min, priming reaction 60~150 minutes, reaction terminated
Afterwards, it takes out after Temperature fall to get 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
Stating pitch and phenolic compound, aldehyde compound, acid is in mass ratio 1:(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),
60~75 DEG C are heated under stirring, isothermal reaction 3~5 hours, pressure was 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 continuation after step (1) compressive reaction is warming up to 390~410 DEG C in a kettle, the constant temperature at -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
State petroleum coke powder, carbonaceous binder, additional adhesive, water mass ratio be 100:(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 press the flow velocity of 0.4~0.5 mL/min
It is passed through vapor, priming reaction 80~120 minutes.
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