CN111377445A - Petroleum coke-based active carbon material and preparation method thereof - Google Patents
Petroleum coke-based active carbon material and preparation method thereof Download PDFInfo
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- 239000002006 petroleum coke Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000003575 carbonaceous material Substances 0.000 title description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 36
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 25
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 25
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 25
- 230000003213 activating effect Effects 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000001994 activation Methods 0.000 claims description 28
- 230000004913 activation Effects 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 239000007787 solid Substances 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000005303 weighing Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 241001070941 Castanea Species 0.000 description 3
- 235000014036 Castanea Nutrition 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 firstly Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a petroleum coke-based activated carbon material and a preparation method thereof, wherein the specific surface area of the activated carbon is 2500-3500 m2(ii)/g; the pore volume is 1.2-1.70 cm3(ii)/g; the iodine adsorption value is 1800-3300 mg/g; the methylene blue adsorption value is 390-700 mg/g. Introducing ammonium phosphate into petroleum coke, and drying and then pretreating; and then mixing the obtained sample with an activating agent, uniformly mixing, activating, washing and drying to obtain the activated carbon. The activated carbon has the advantages of high specific surface area, high pore volume, concentrated pore size distribution, excellent adsorption performance and the like, and is low in production cost and small in environmental pollution.
Description
Technical Field
The invention relates to a carbon material and a preparation method thereof, in particular to an activated carbon material prepared by taking petroleum coke as a raw material and a preparation method thereof.
Background
The newly revised atmospheric pollution control law of the people's republic of China, executed from 1 month and 1 day 2016, requires the establishment of a stricter petroleum coke standard, and the new petroleum coke standard NB/SH/T0527-2015 strictly limits the sulfur content of petroleum coke: the highest value is not more than 3 wt%. This means that "petroleum coke with a sulfur content greater than 3 wt.% is regulated for sale, import and use.
Taking the China petrochemical industry as an example, the total capacity of the delayed coking device of the enterprise is 3900 ten thousand tons/year, the petroleum coke yield is about 1100 ten thousand tons/year, and the high-sulfur petroleum coke exceeds 700 ten thousand tons/year. In the face of such a large amount of high-sulfur petroleum cokes, the search for a low-cost, clean and efficient high-sulfur petroleum coke utilization technology improves economic benefits, and becomes an urgent need for Chinese petrochemical refining enterprises. The petroleum coke, particularly the high-sulfur petroleum coke, is used for preparing the high-value-added activated carbon product, so that higher economic benefit can be obtained, and a new route with good economic and social benefits can be developed for the utilization of the high-sulfur petroleum coke.
At present, one of the main routes for preparing activated carbon with high specific surface area by using petroleum coke as a raw material is to prepare the activated carbon by using potassium hydroxide as an activating agent and using a chemical activation method. Chinese patent CN00104267.X uses petroleum coke or asphalt as raw material, KOH as activating agent, and when the alkali-carbon ratio (KOH/petroleum coke mass ratio) is 4:1, the specific surface area is as high as 2308m2Per gram of activated carbon. Chinese patent CN1304788A mixes KOH and petroleum coke according to the proportion of 5:1, and activates at high temperature to prepare the product with the specific surface area of more than 3500m2Per gram of activated carbon. However, the method has the disadvantages of large alkali-coke ratio, high production cost, serious environmental pollution, low activation yield, high carbon consumption, wide pore size distribution of the obtained activated carbon and limited application range.
At present, the heating modes for preparing the activated carbon mainly comprise two modes: 1. a traditional heating mode, 2, a microwave heating mode. The patent publication for preparing activated carbon by traditional heating method includes CN200610123444.X, CN201210246423.2 and CN 201721302233.2. CN200610123444.X adopts coal-based activated carbon with high specific surface area prepared by anthracite as raw material and KOH as activating agent, and the preparation method takes 2-5 hours at 600-880 ℃; CN201210246423.2 adopts chestnut shells as raw materials and zinc chloride as an activating agent to obtain chestnut shell activated carbon with high adsorption performance, and the chestnut shell activated carbon also needs to react for 60-90 minutes at 300-550 ℃, and published patents for preparing the activated carbon by using a microwave heating mode include CN 201610049050.8, CN 201711284823.1, CN 201711306302.1 and the like, and compared with the traditional heating mode, the microwave heating mode has the advantages of short reaction time, low energy consumption and the like. The dielectric constant of the petroleum coke is in a fluctuation state in the microwave field, so that the wave absorbing performance of the petroleum coke is obviously changed, and the petroleum coke is heated unevenly; the microwave heating material is heated from the inside to the outside of the material, so that temperature gradient is easily generated in the material, and the material is also heated unevenly; the power size of microwave has great influence to the speed of heating, and power is big, and the unit interval material absorbs microwave energy more, and it is many to produce the heat, but power is too big, can be with material overheat in short time, and the central part is heated and is concentrated and the intensification is faster, and the speed that unnecessary heat conduction was conducted the surface can't catch up with thermal accumulation to make the material be heated unevenly easily, lead to the material to explode and spout. The uneven heating of the material can lead to uneven distribution of the aperture of the active carbon, which can affect the quality of the active carbon when being serious, and the explosion spraying of the material can obviously reduce the yield of the active carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a petroleum coke-based activated carbon material and a preparation method thereof. The activated carbon material obtained by the method has the advantages of high specific surface area, high pore volume, excellent adsorption performance and the like, and the preparation method is simple.
The invention provides a preparation method of petroleum coke-based activated carbon, which comprises the following steps:
(1) introducing ammonium phosphate into the petroleum coke, and then drying;
(2) pretreating the sample obtained in the step (1) by using vapor-containing gas;
(3) mixing the sample obtained in the step (2) with an activating agent, uniformly mixing, placing the material in a microwave-light wave reactor, and activating under the condition of nitrogen or inert atmosphere;
(4) and (4) washing and drying the activated sample obtained in the step (3) to obtain the activated carbon.
In the preparation method of the petroleum coke-based activated carbon, the ammonium phosphate in the step (1) is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and preferably ammonium phosphate.
In the preparation method of the petroleum coke-based activated carbon, the method for introducing the ammonium phosphate into the petroleum coke in the step (1) is carried out according to a method known in the art, and comprises one or more of an equal-volume impregnation method, a supersaturated impregnation method and a kneading method, and the supersaturated impregnation method is preferred.
In the preparation method of the petroleum coke-based activated carbon, the drying temperature in the step (1) is 60-150 ℃, the preferred drying temperature is 80-120 ℃, the drying time is 2-8 hours, and the preferred drying time is 4-6 hours. The drying is further preferably carried out under vacuum conditions.
In the preparation method of the petroleum coke-based activated carbon, the mass ratio of the ammonium phosphate salt to the petroleum coke in the step (1) is 0.05-1: 1, preferably 0.2-0.8: 1.
In the preparation method of the petroleum coke-based activated carbon, the steam-containing gas in the step (2) is steam or mixed gas of steam and carrier gas, and the volume ratio of the steam to the carrier gas in the mixed gas is 1: 20-1: 1, preferably 1: 10-1: 2; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the preparation method of the petroleum coke-based activated carbon, the specific pretreatment process in the step (2) comprises a first-stage pretreatment process, a second-stage pretreatment process and a cooling process, wherein the first-stage pretreatment process is carried out at the temperature of 150-250 ℃, preferably 180-220 ℃, and the pretreatment time is 1-6 hours, preferably 2-4 hours; the second-stage pretreatment temperature is 300-500 ℃, preferably 350-450 ℃, the pretreatment time is 1-6 hours, preferably 2-4 hours, and then the second-stage pretreatment is cooled to 20-100 ℃, preferably 40-80 ℃; the cooling process is preferably carried out under nitrogen protection.
In the preparation method of the petroleum coke-based activated carbon, the volume space velocity of the vapor-containing gas in the step (2) is 500-2000 h-1。
In the preparation method of the petroleum coke-based activated carbon, the activation process in the step (3) is specifically operated as follows: uniformly mixing the sample obtained in the step (2) with an activating agent, placing the material into a microwave-light wave reactor after uniform mixing, heating to an activation temperature under nitrogen or inert atmosphere, and cooling to 20-100 ℃ after activation for subsequent treatment, wherein the inert atmosphere is one or more of helium or argon; the activation temperature is 600-1000 ℃, preferably 700-900 ℃, and the activation time is 5-60 min, preferably 10-30 min; the microwave frequency is 2450 MHz; the microwave power is 1-10 kw, preferably 2-4 kw, and the light wave power is 0.8-20 kw, preferably 1-8 kw per kg of petroleum coke.
In the preparation method of the petroleum coke-based activated carbon, the microwave-light wave reactor in the step (3) is provided with a light wave generator at the upper part of the microwave reactor, light emitted by the light wave generator is reflected and focused by a reflector to realize the heating of materials, and the light wave heats the materials from the outside to the inside.
In the preparation method of the petroleum coke-based activated carbon, the activating agent in the step (3) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and the activating agent is preferably potassium hydroxide.
In the preparation method of the petroleum coke-based activated carbon, the mass ratio of the sample obtained in the step (2) in the step (3) to the activating agent is 1: 0.5-6, preferably 1:2 to 4.
In the preparation method of the petroleum coke-based activated carbon, the washing process in the step (4) is as follows: firstly, mixing the sample obtained in the step (3) with an aqueous solution with a pH value not more than 7, preferably grinding the sample obtained in the step (3) into powder, mixing the powder with the aqueous solution with a pH value not more than 7, uniformly mixing, and carrying out solid-liquid separation until the pH value of the filtrate is neutral. The mass ratio of the sample obtained in the step (3) to the aqueous solution is 1: 5-1: 30, and preferably 1: 10-1: 20.
In the preparation method of the petroleum coke-based activated carbon, the drying temperature in the step (4) is 60-150 ℃, the preferable drying temperature is 80-120 ℃, the drying time is 2-10 hours, and the preferable drying time is 4-8 hours; the drying is preferably carried out under vacuum.
The second aspect of the invention provides petroleum coke-based activated carbon prepared by the method, and the specific surface area of the petroleum coke-based activated carbon is 2500-3500 m2(ii)/g; the pore volume is 1.2-1.70 cm3(ii)/g; the iodine adsorption value is 1800-3300 mg/g; the methylene blue adsorption value is 390-700 mg/g. Compared with the prior art, the petroleum coke-based active carbon material and the preparation method thereof have the following advantages:
1. according to the preparation method of the petroleum coke-based active carbon material, firstly, petroleum coke is pretreated, ammonium phosphate is introduced into the petroleum coke, then, steam-containing gas is adopted to treat the petroleum coke, so that the ammonium phosphate is promoted to be decomposed in the petroleum coke to generate ammonia gas and phosphoric acid, the generated ammonia gas provides more primary pores for further activation of the petroleum coke, and meanwhile, the generated phosphoric acid can also be used as an activating agent to carry out primary activation on the petroleum coke, so that a developed pore structure is created. Solves the problems of serious equipment corrosion and higher production cost caused by that petroleum coke has compact structure, high crystallinity, lacks of primary pores required by activation and needs to adopt strong base with large base-coke ratio to activate pore-forming in inert atmosphere.
2. In the preparation method of the petroleum coke-based activated carbon material, phosphoric acid generated by decomposing ammonium phosphate salt plays a primary activation role on petroleum coke, and then the subsequent activation of the activating agent is carried out, so that the activation effect is improved, the consumption of the alkali activating agent can be further reduced, the production cost is greatly reduced, and the environmental pollution is small.
3. In the preparation method of the petroleum coke-based activated carbon material, the activation process is carried out under the microwave-light wave heating condition, and the microwave-light wave coupling heating mode can ensure that the material is heated more uniformly on the basis of keeping the advantages of the microwave heating mode, and simultaneously solves the problem of material explosion caused by overhigh microwave heating power when being independently adopted, so that the quality of the activated carbon product is obviously improved. The light wave is formed by arranging a light wave generator on the upper part of the microwave reaction kettle, light emitted by the light wave generator is reflected and focused by a reflector to heat materials, and the heating mode of the light wave to the materials is from outside to inside.
4. The specific surface area of the petroleum coke-based active carbon material prepared by the method is close to 3500m2G, rich micropores and excellent adsorption performance.
Detailed Description
The technical contents and effects of the present invention will be further described with reference to examples, but the present invention is not limited thereto.
In the following examples and comparative examples, low temperature N was used for the specific surface area and pore size distribution of the samples2Measured by an adsorption method.
Example 1
Dissolving 40g of ammonium phosphate in 150mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 120 ℃ for 5 h. Pretreating the dried solid sample for 3h at 200 ℃ by using mixed gas of water vapor and argon gas in a volume ratio of 1:5 (the volume space velocity of the mixed gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium bicarbonate are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.5kw, the lightwave power is 0.5kw, and the temperature is raised to 800 ℃ under the nitrogen atmosphere for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-1.
Example 2
Weighing 40g of ammonium phosphate, and dissolving the ammonium phosphate in 150mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 120 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And raising the temperature to 450 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium hydroxide are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.5kw, the lightwave power is 0.5kw, and the temperature is raised to 950 ℃ under the nitrogen atmosphere for activation for 40 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-2.
Example 3
Weighing 40g of ammonium hydrogen phosphate, and dissolving in 150mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 120 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 800 h)-1) Then the temperature is increased to 400 ℃, the pretreatment is continued for 3 hours, and then the mixture is cooled to 40 ℃ under the protection of nitrogen to obtain a pretreatmentAnd marble oil coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium hydroxide are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.5kw, the lightwave power is 0.5kw, and the temperature is raised to 700 ℃ under the nitrogen atmosphere for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-3.
Example 4
Weighing 20g of ammonium phosphate, and dissolving the ammonium phosphate in 150mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left for 1h, then filtered, and the resulting solid sample was dried in an oven at 120 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium hydroxide are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.5kw, the lightwave power is 0.5kw, and the temperature is raised to 900 ℃ under the nitrogen atmosphere for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-4.
Example 5
Weighing 40g of ammonium phosphateDissolving in 150mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left for 1h, then filtered, and the resulting solid sample was dried in an oven at 120 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And raising the temperature to 400 ℃, continuing to pretreat for 4 hours, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium hydroxide are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.3kw, the lightwave power is 0.7kw, and the temperature is raised to 900 ℃ under the nitrogen atmosphere for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-5.
Example 6
Weighing 40g of ammonium phosphate, and dissolving the ammonium phosphate in 150mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left for 1h, then filtered, and the resulting solid sample was dried in an oven at 120 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium hydroxide are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.5kw, the lightwave power is 0.5kw, and the temperature is raised to 800 ℃ under the nitrogen atmosphere for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-6.
Example 7
Weighing 40g of ammonium phosphate, and dissolving the ammonium phosphate in 150mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left for 1h, then filtered, and the resulting solid sample was dried in an oven at 120 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h)-1) And then raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium hydroxide are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.7kw, the lightwave power is 0.3kw, and the temperature is raised to 700 ℃ under the nitrogen atmosphere for activation for 50 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-7.
Comparative example 1
Grinding 100g of petroleum coke into powder, then uniformly mixing the powder with 400g of potassium bicarbonate, placing the mixture into a microwave-lightwave reactor, wherein the frequency of a microwave in the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.5kw, and the lightwave power is 0.5kw, and heating the mixture to 800 ℃ in a nitrogen atmosphere for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-1.
Comparative example 2
Weighing 40g of ammonium phosphate, and dissolving the ammonium phosphate in 150mL of deionized water to obtain a solution A; grinding 100g of petroleum coke into powder, adding the powder into the solution A, standing for 1.5h, filtering, and drying the obtained solid sample in an oven at 120 ℃ for 5h to obtain the pretreated petroleum coke.
100g of the pretreated petroleum coke obtained above and 400g of potassium bicarbonate are uniformly mixed and placed in a microwave-lightwave reactor, the frequency of the microwave of the reactor is 2450MHz, the total power is 1kw, the microwave power is 0.5kw, the lightwave power is 0.5kw, and the temperature is raised to 800 ℃ under the nitrogen atmosphere for activation for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the petroleum coke-based activated carbon, which is marked as C-1.
The properties of the petroleum coke-based activated carbon obtained in the examples and comparative examples are shown in table 1.
TABLE 1 Properties of Petroleum Coke-based activated carbon
Claims (16)
1. A preparation method of petroleum coke-based activated carbon material comprises the following steps:
(1) introducing ammonium phosphate into the petroleum coke, and then drying;
(2) pretreating the sample obtained in the step (1) by using vapor-containing gas;
(3) mixing the sample obtained in the step (2) with an activating agent, uniformly mixing, placing the material in a microwave-light wave reactor, and activating under the condition of nitrogen or inert atmosphere;
(4) and (4) washing and drying the activated sample obtained in the step (3) to obtain the activated carbon.
2. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the ammonium phosphate in the step (1) is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and preferably ammonium phosphate.
3. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the method for introducing the ammonium phosphate into the petroleum coke in the step (1) is one or more of an isometric impregnation method, a supersaturated impregnation method and a kneading method, and the supersaturated impregnation method is preferred.
4. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the drying temperature in the step (1) is 60-150 ℃, the preferred drying temperature is 80-120 ℃, the drying time is 2-8 hours, and the preferred drying time is 4-6 hours; the drying is further preferably carried out under vacuum conditions.
5. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the mass ratio of the ammonium phosphate to the petroleum coke in the step (1) is 0.05-1: 1, preferably 0.2-0.8: 1.
6. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the water vapor-containing gas in the step (2) is water vapor or a mixed gas of water vapor and a carrier gas, and the volume ratio of the water vapor to the carrier gas in the mixed gas is 1: 20-1: 1, preferably 1: 10-1: 2; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
7. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the specific process of the pretreatment in the step (2) comprises a first-stage pretreatment, a second-stage pretreatment and cooling, wherein the temperature of the first-stage pretreatment is 150-250 ℃, the preferred temperature is 180-220 ℃, and the pretreatment time is 1-6 hours, and the preferred time is 2-4 hours; the second-stage pretreatment temperature is 300-500 ℃, the preferred temperature is 350-450 ℃, the treatment time is 1-6 hours, the preferred time is 2-4 hours, and then the second-stage pretreatment temperature is cooled to 20-100 ℃, and the preferred time is 40-80 ℃; the cooling process is preferably carried out under nitrogen protection.
8. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the volume space velocity of the vapor-containing gas in the step (2) is 500-2000 h-1。
9. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the activation process in step (3) is specifically operated as follows: uniformly mixing the sample obtained in the step (2) with an activating agent, placing the material into a microwave-optical wave reactor after uniform mixing, activating under the condition of inert atmosphere, heating to an activation temperature under the condition of nitrogen or inert atmosphere, and cooling to 20-100 ℃ after activation for subsequent treatment, wherein the inert atmosphere is one or more of helium or argon; the activation temperature is 600-1000 ℃, preferably 700-900 ℃, and the activation time is 5-60 min, preferably 10-30 min; the microwave frequency is 2450 MHz; the microwave power is 1-10 kw per kg of petroleum coke, and preferably 2-4 kw; the light wave power is 0.8-20 kw, preferably 1-8 kw.
10. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the activating agent in the step (3) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and preferably potassium hydroxide.
11. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the mass ratio of the sample obtained in the step (2) to the activating agent in the step (3) is 1: 0.5-6, preferably 1:2 to 4.
12. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the washing process in the step (4) is as follows: firstly, mixing the sample obtained in the step (3) with an aqueous solution with a pH value not more than 7, preferably grinding the sample obtained in the step (3) into powder, mixing the powder with the aqueous solution with a pH value not more than 7, uniformly mixing, and carrying out solid-liquid separation until the pH value of the filtrate is neutral.
13. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 12, characterized in that: the mass ratio of the sample obtained in the step (3) to the aqueous solution is 1: 5-1: 30, and preferably 1: 10-1: 20.
14. A process for the preparation of a petroleum coke-based activated carbon material as claimed in claim 1, characterized in that: the drying temperature in the step (4) is 80-200 ℃, the preferable drying temperature is 120-180 ℃, the drying time is 2-10 hours, and the preferable drying time is 4-8 hours; the drying is preferably carried out under vacuum.
15. A petroleum coke-based activated carbon is characterized in that: the activated carbon is prepared by the method of any one of claims 1 to 14.
16. A petroleum coke-based activated carbon as claimed in claim 15 wherein: a petroleum coke-based activated carbon is characterized in that: the specific surface area of the petroleum coke-based activated carbon is 2500-3500 m2(ii)/g; the pore volume is 1.2-1.70 cm3(ii)/g; the iodine adsorption value is 1800-3300 mg/g; the methylene blue adsorption value is 390-700 mg/g.
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