CN116730338A - Activated carbon, preparation method and application thereof, mercury removal activated carbon, and preparation method and application thereof - Google Patents
Activated carbon, preparation method and application thereof, mercury removal activated carbon, and preparation method and application thereof Download PDFInfo
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- CN116730338A CN116730338A CN202210218476.7A CN202210218476A CN116730338A CN 116730338 A CN116730338 A CN 116730338A CN 202210218476 A CN202210218476 A CN 202210218476A CN 116730338 A CN116730338 A CN 116730338A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 367
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims description 59
- 229910052753 mercury Inorganic materials 0.000 title claims description 56
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000003245 coal Substances 0.000 claims abstract description 49
- 230000003213 activating effect Effects 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000005539 carbonized material Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000012778 molding material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 230000004913 activation Effects 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 19
- 239000003607 modifier Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- -1 ammonium halide salt Chemical class 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000011294 coal tar pitch Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 235000013379 molasses Nutrition 0.000 claims description 2
- 239000011301 petroleum pitch Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 17
- 239000010881 fly ash Substances 0.000 abstract description 10
- 238000007885 magnetic separation Methods 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000005415 magnetization Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000002956 ash Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000002006 petroleum coke Substances 0.000 description 6
- 230000035515 penetration Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001622 calcium bromide Inorganic materials 0.000 description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 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
- C01B32/336—Preparation characterised by gaseous activating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of activated carbon preparation, and particularly relates to activated carbon, a preparation method and application thereof, and mercury-removing activated carbon, and a preparation method and application thereof. The preparation method of the activated carbon is characterized by comprising the following steps: crushing and screening coal liquefaction residues to obtain raw material powder; mixing the raw material powder with an adhesive, and performing molding treatment to obtain a molding material; pre-oxidizing the molding material by an oxidant to obtain an oxidized material; carbonizing the oxidized material in the presence of protective atmosphere to obtain carbonized material and carbonized tail gas; and activating the carbonized material by an activating agent to obtain the activated carbon. The activated carbon is prepared by taking coal liquefaction residues as raw materials, and has developed specific surface area and pore structure. The prepared activated carbon has magnetism, and can be separated from fly ash by magnetic separation.
Description
Technical Field
The invention belongs to the technical field of activated carbon preparation, and particularly relates to activated carbon, a preparation method and application thereof, and mercury-removing activated carbon, and a preparation method and application thereof.
Background
China is the largest coal production and consumption country in the world, and in the future, the energy structure of China is still mainly based on coal. At present, the thermal power generating unit of the fire coal accounts for more than 70% of the capacity of the general assembly machine in China, the proportion is still more than 50% in 2050, the fire coal power generation provides the firmest power guarantee for the economic and social development of China and the life of people, but simultaneously, a large amount of pollutants such as smoke dust, sulfur dioxide, nitrogen oxides, carbon dioxide, heavy metals and the like are discharged, and the pollutants cause a series of ecological environment and human health problems. With the progress of pollution control technology, main pollutants of coal-fired power plants are smoke dust and SO 2 And NO x Etc. have been well controlled, while heavy metal contaminants such as mercury have not been treated effectively.
Mercury has high toxicity, nondegradability and bioaccumulation, and can produce long-term harm to ecological environment and crowd health, and governments around the world are very important in mercury pollution control. The mercury emission concentration of the non-low-rank coal and the low-rank coal for the combustion of the active service unit is 1.8 mu g/m and 16.5 mu g/m respectively 3 The mercury emission concentration of the non-low-rank coal and the low-rank coal for the combustion of the newly-built service unit is 0.028 and 5.528 mu g/m respectively 3 。
Mercury exists in the flue gas of power plants mainly in three forms: particulate mercury (Hg) p ) Elemental mercury (Hg) 0 ) And combined mercury (Hg) 2+ And Hg of + ). The granular mercury can be effectively captured by the dust removal system; combined mercury (Hg) 2+ And Hg of + ) Due to the characteristic of water solubility, the water can be effectively removed by a desulfurization system; but due to elemental mercury (Hg) 0 ) Easy to existThe characteristics of volatilization (higher saturated vapor pressure), poor water solubility, stable chemical property and the like are difficult to be effectively trapped by the current pollution control equipment, and how to remove elemental mercury becomes the key point and the difficulty of mercury control of coal-fired flue gas.
The pore structure, specific surface area and surface property of the activated carbon have great influence on the mercury removal performance of the activated carbon, and the mercury has high volatility and weak binding property on the surface of the carbon, so that the mercury removal capacity of the common activated carbon is weak. At present, the activated carbon is often modified by a chemical method, which can improve the mercury adsorption capacity of the activated carbon, and mainly comprises the following steps: heavy metal modification (gold loading and silver loading), sulfuration modification (sulfuration), halogenation modification (chlorine permeation, iodine permeation and bromine permeation), catalytic oxidation modification and the like are carried out to improve the mercury removal capability of the activated carbon.
At present, the activated carbon injection technology is considered as the most potential mercury emission control method, and the activated carbon injection adsorption method is to inject activated carbon before a particle catcher (an electric dust collector or a bag-type dust collector), so that part of mercury in the flue gas is adsorbed by the injected activated carbon and then is trapped by the dust catcher. The method has the advantages that the smoke discharge amount of the coal-fired power plant is large, the mercury concentration in the smoke is low, the retention time of the activated carbon is short, the consumption of the activated carbon is excessive, and meanwhile, the carbon content in the fly ash is increased due to the fact that a large amount of activated carbon is sprayed, the quality of the fly ash is reduced, the follow-up utilization of the fly ash is affected, and the application of the technology is limited. Therefore, the key of the coal-fired flue gas injection mercury removal technology is to develop the mercury removal activated carbon with high efficiency.
CN101844074a discloses a method for preparing active carbon, which comprises the following steps: the method comprises the following specific steps: the raw material coal is selected from Taixi anthracite with 7.64% of water, 5.30% of ash, 8.59% of volatile matter and 78.47% of fixed carbon, and the weight ratio is as follows: coal dust: and (2) an adhesive: water=69-73%: 22-25%:5-7%, performing anaerobic carbonization in a calciner at 300-400 ℃ for 40min, enabling volatile matters of raw materials to reach 5-7% after anaerobic carbonization, then feeding into a pulverizer for pulverizing, enabling the granularity after pulverizing to be more than or equal to 90% in a tar dewatering tank, adding an adhesive, stirring in a kneader, feeding into a strip extruder for strip extrusion molding, feeding into a carbonization furnace for carbonization, feeding into an activation furnace for activation, feeding into a pulverizer for pulverizing, enabling granularity after pulverizing to be more than or equal to 90% in a soaking device for soaking, and enabling the amount of calcium bromide loaded at the moment to be the raw material content: not less than 0.5%, and the values of the parameters of the finished product are as follows: iodine value: 700-800mg/g; DYE adsorption value: 7-11mg/g; the impregnated calcium bromide amount is more than or equal to 0.5%, the micropore volume is more than or equal to 0.4ml/g, and the mercury adsorption capacity is more than or equal to 0.3mg/g.
CN109970057a discloses a method for preparing activated carbon from coal liquefaction residue powder, semi-coke powder, auxiliary carbonaceous materials, water, organic binder, inorganic and organic binder and the like by mixing, kneading, forming, pre-oxidizing, carbonizing and activating. The method utilizes inorganic salts in the coal liquefaction residues, effectively improves the mechanical compressive strength of the honeycomb activated carbon on the premise of not affecting the specific surface area of the product, overcomes the characteristic of non-cohesiveness or weak cohesiveness of the semi-coke powder, effectively utilizes the advantages of low ash content and high carbon content, reduces the cost of the activated carbon raw materials, and improves the overall benefit of the coal liquefaction process.
CN102153081a discloses a method for preparing activated carbon by directly liquefying residue from coal, which comprises mixing liquefied residue powder with KNO 3 Mixing KOH and absolute ethyl alcohol, drying, pre-oxidizing, carbonizing and activating to obtain coarse active carbon, and then pickling and deashing to obtain the finished active carbon.
CN105712347a discloses a method for preparing sulfur-rich activated carbon from high sulfur petroleum coke. Mixing potassium hydroxide and high-sulfur petroleum coke according to a proportion, and uniformly stirring; calcining and activating the mixture, collecting hydrogen sulfide gas generated in the calcining and activating process, cooling, washing with water, drying to obtain powdery active carbon, reacting the hydrogen sulfide gas generated in the activating process with sulfur dioxide gas generated by directly burning high-sulfur petroleum coke to generate elemental sulfur, dipping active carbon particles in dipping solution prepared by the elemental sulfur, and drying to obtain the sulfur-enriched active carbon.
The method disclosed in CN105712347a has the main drawbacks: 1. the potassium hydroxide and the high-sulfur petroleum coke are mixed according to the proportion, and in the process of calcining and activating the activated carbon, the alkali metal hydroxide plays a role in desulfurizing the petroleum coke, so that the sulfur content of the petroleum coke is greatly reduced; 2. in the flue gas mercury removal process, a large amount of activated carbon is sprayed to raise the carbon content in the fly ash, so that the quality of the fly ash is reduced, and the subsequent utilization of the fly ash is affected.
The coal liquefaction residue is an inevitable byproduct in the direct coal liquefaction process, is a high-carbon, high-sulfur and high-ash substance, and mainly comprises unconverted coal organisms, inorganic minerals and an additional liquefaction catalyst in the liquefied raw material coal, wherein the mass of the coal liquefaction residue accounts for 20-40% of the direct coal liquefaction product. Because the coal liquefaction residues are rich in heavy carbon and high molecular aromatic structures, the coal liquefaction residues are easy to polymerize or crosslink, so that the coal liquefaction residues can be used as precursor materials of high-performance carbon materials.
At present, research on producing activated carbon by using liquefied residues as raw materials is concentrated on a chemical method, and alkali metal hydroxide (KOH) is often used as an active agent, and the process mainly comprises the steps of preparing the activated carbon with high specific surface area, wherein although a mixture of the alkali metal hydroxide and the liquefied residues is heated in an inert atmosphere to enrich pore structures of the liquefied residues, the alkali metal hydroxide plays a role in desulfurizing the liquefied residues at the same time, so that the sulfur content in the activated carbon is reduced, and the method also has the defects of long process route, high cost, serious corrosion to equipment and the like.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provides activated carbon, a preparation method and application thereof, mercury-removing activated carbon, and a preparation method and application thereof. The preparation method takes coal liquefaction residues as raw materials to prepare the activated carbon. The active carbon is excellent in specific surface area and pore structure; by adopting the preparation method, elemental sulfur is enriched on the surface of the active carbon, and sulfur-containing adsorption sites on the surface are increased. The prepared activated carbon has magnetism, and can be separated from substances such as fly ash by magnetic separation.
In order to achieve the above object, a first aspect of the present invention provides a method for producing activated carbon, characterized in that the method comprises the steps of:
(1) Crushing and screening coal liquefaction residues to obtain raw material powder;
(2) Mixing the raw material powder with an adhesive, and performing molding treatment to obtain a molding material;
(3) Pre-oxidizing the molding material by an oxidant to obtain an oxidized material;
(4) Carbonizing the oxidized material in the presence of protective atmosphere to obtain carbonized material and carbonized tail gas;
(5) And activating the carbonized material by an activating agent to obtain the activated carbon.
The second aspect of the invention provides an activated carbon prepared by the above method.
The third aspect of the invention provides application of the activated carbon in the mercury removal field.
The fourth aspect of the invention provides a method for preparing mercury-removing active carbon, which is characterized in that,
modifying the activated carbon by using a modifier to obtain mercury-removing activated carbon;
wherein the activated carbon is the activated carbon provided in the second aspect of the invention.
The fifth aspect of the invention provides the mercury-removing activated carbon prepared by the preparation method of the mercury-removing activated carbon.
The sixth aspect of the invention provides an application of the mercury removal activated carbon in the mercury removal field.
Through the technical scheme, the activated carbon and the preparation method and application thereof, and the mercury-removing activated carbon and the preparation method and application thereof have the following beneficial effects:
the active carbon prepared by taking the coal liquefaction residues as raw materials not only has higher surface area, but also has excellent pore structure. By adopting the raw materials and the preparation process, the surface of the activated carbon is enriched with elemental sulfur, so that sulfur-containing adsorption sites on the surface of the activated carbon are increased, and the mercury adsorption capacity of the activated carbon can be improved. The prepared activated carbon has magnetism, and the activated carbon after mercury adsorption can be separated from fly ash through magnetic separation.
Further, the activated carbon is chemically modified by adopting ammonium halide salt, so that the mercury adsorption capacity of the activated carbon is further improved.
Drawings
FIG. 1 is a schematic process flow diagram of a method for preparing activated carbon.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In order to achieve the above object, a first aspect of the present invention provides a method for producing activated carbon, characterized in that the method comprises the steps of:
(1) Crushing and screening coal liquefaction residues to obtain raw material powder;
(2) Mixing the raw material powder with an adhesive, and performing molding treatment to obtain a molding material;
(3) Pre-oxidizing the molding material by an oxidant to obtain an oxidized material;
(4) Carbonizing the oxidized material in the presence of protective atmosphere to obtain carbonized material and carbonized tail gas;
(5) And activating the carbonized material by an activating agent to obtain the activated carbon.
In the invention, the activated carbon is prepared by taking the coal liquefaction residues as raw materials, and the activated carbon has excellent specific surface area and pore structure; by adopting the preparation method, elemental sulfur is enriched on the surface of the active carbon, and sulfur-containing adsorption sites on the surface are increased.
According to the invention, the content of fixed carbon in the coal liquefaction residue is 45-50wt% and the content of ash is 15-25wt%.
According to the invention, the content of iron-containing substances in the coal liquefaction residues is 0.45-1wt%, and the content of sulfur-containing substances is 2-4wt%.
In the invention, the main existence form of iron in the liquefied residue is Fe 2 O 3 High-valence ferric salt liquidThe carbon in the residue has catalytic activation effect, and is beneficial to pore formation of the activated carbon in the activation reaction. In the final active carbon product, iron element is mostly Fe 3 O 4 The activated carbon exhibits good magnetic properties, and can be separated from the fly ash by magnetic separation.
In the invention, the mercury penetration adsorption capacity of the coal liquefaction residues is 0.3-3 (120 ℃ C./(mg/g), and the specific magnetization rate is 6-13cm 3 /g。
In the present invention, the above-described mercury penetration adsorption amount and specific magnetization ratio of the coal liquefaction residue are not limited to the coal liquefaction residue in the present invention, but are only used to represent the difference between the performance of the mercury penetration adsorption amount and specific magnetization ratio of the coal liquefaction residue used in the present invention and the mercury penetration adsorption amount and specific magnetization ratio of the activated carbon and the demercuration activated carbon prepared therefrom.
In the invention, the particle size of the raw material powder is 120-200 meshes.
According to the invention, the mass ratio of the raw material powder to the binder is 100:5-20.
Further, the mass ratio of the raw material powder to the binder is 100:10-15.
According to the invention, the binder is at least one selected from the group consisting of coal tar pitch, petroleum pitch, sulfurous acid pulp waste liquid, molasses liquid, starch liquid and carboxymethyl cellulose solution.
According to the invention, the oxidant is a gas mixture containing oxygen, and the oxygen content is less than or equal to 10vol% based on the total volume of the gas mixture.
According to the invention, the pre-oxidation temperature is 120-250 ℃.
In the invention, the pre-oxidation is in the temperature range, so that the subsequent activation time can be shortened, and the subsequent activation temperature can be reduced.
Further, the pre-oxidation temperature is 180-220 ℃.
According to the invention, the pre-oxidation time is 0.5-3 hours.
Further, the pre-oxidation time is 1-2h.
According to the invention, the carbonization temperature is 500-650 ℃.
Further, the carbonization temperature is 550-600 ℃.
According to the invention, the carbonization time is 0.5-2h.
Further, the carbonization time is 1-1.5h.
According to the invention, the heating rate of the carbonization is 1-20 ℃/min.
In the invention, the heating rate of carbonization is in the range, excessive tar and coal gas separated out in the carbonization process can be effectively avoided, the yield of the activated carbon can be improved, the adsorption performance of the prepared activated carbon can be enhanced, and the product activated carbon has better mercury adsorption performance.
Further, the heating rate of the carbonization is 5-10 ℃/min.
According to the invention, the activator comprises an activating gas and a non-activating gas, the activating gas comprises water vapor, CO 2 、SO 2 Is a mixed gas of (a) and (b).
In the present invention, the inert gas is a gas that does not react with the carbonized material, and nitrogen may be selected, for example.
In the invention, under the action of carbon in the activated carbon and an activator, residual iron in the liquefied residue is gradually converted into Fe 3 O 4 。
According to the invention, the water vapor in the activated gas: CO 2 ：SO 2 The volume ratio of (2) is 20-50:20-40:1.
Further, water vapor in the activated gas: CO 2 ：SO 2 30-40:20-30:1.
According to the invention, the activating gas is present in a proportion of 5 to 40% by volume, based on the total volume of the activator.
Further, the activating gas is present in an amount of 20 to 30vol% based on the total volume of the activating agent.
According to the invention, SO in the activator 2 And (3) burning the carbonized tail gas. The activated gas has water vapor and carbon dioxide content which are not satisfiedSufficient to be replenished from the activator replenishment port.
According to the invention, the activation temperature is 750-950 ℃.
The activation temperature is too low, and the specific surface area and pore structure of the prepared activated carbon are deteriorated; however, the activation temperature is too high, the specific surface area of the prepared activated carbon is reduced, the pore structure of the activated carbon is deteriorated due to collapse of the pore channel structure, and the problems of reduced sulfur content, reduced yield and the like of the activated carbon occur at the same time, so that the performance of the activated carbon for adsorbing mercury is finally reduced.
Further, the activation temperature is 850-900 ℃.
According to the invention, the activation time is 0.5-5h.
In the invention, the carbonized material is burnt to obtain the corresponding pore structure by utilizing the thermal destruction performance of the activator under the high temperature condition. By adjusting the conditions of the proportion of the activating agent, the activating temperature and the like, the reaction of the activating gas and the carbonized material can be regulated and controlled, and the proportion of new holes to old holes in the activating process is different, so that the activated carbon with proper pore structure is obtained.
Further, the activation time is 2-3 hours.
According to the invention, the temperature rise rate of the activation is 5-10 ℃/min.
According to the invention, the activated carbon is crushed and sieved to obtain the fine activated carbon.
Further, the particle size of the fine activated carbon is 100-400 mesh.
The invention also provides the active carbon prepared by the method.
According to the invention, the specific surface area of the activated carbon is 500-1000m 2 /g; the aperture is 1.5-5nm.
In the invention, different application fields have different requirements on the pore structure of the activated carbon. The pore diameter of the activated carbon is matched with the geometric size of the adsorbate molecules or ions, and when the ratio of the pore diameter of the activated carbon to the diameter of the adsorbate molecules is 1.7-3:1, the adsorbent utilization rate is highest.
The third aspect of the invention provides application of the activated carbon in the mercury removal field.
The prepared activated carbon can be applied to removing mercury in flue gas generated in the fields of coal-fired power plants, coal-fired boilers, garbage incineration and the like.
The fourth aspect of the invention provides a method for preparing mercury-removing active carbon, which is characterized in that,
modifying the activated carbon by using a modifier to obtain mercury-removing activated carbon;
wherein the activated carbon is the activated carbon provided in the second aspect of the invention.
In one specific embodiment of the invention, the preparation method of the mercury removal activated carbon comprises the following steps:
(1) Crushing and screening coal liquefaction residues to obtain raw material powder;
(2) Mixing the raw material powder with an adhesive, and performing molding treatment to obtain a molding material;
(3) Pre-oxidizing the molding material by an oxidant to obtain an oxidized material;
(4) Carbonizing the oxidized material in the presence of protective atmosphere to obtain carbonized material and carbonized tail gas;
(5) Activating the carbonized material by an activating agent to obtain activated carbon;
(6) Modifying the activated carbon by using a modifier to obtain the mercury-removing activated carbon.
According to the invention, the modifier is an aqueous solution of an ammonium halide salt.
According to the invention, the activated carbon is chemically modified by adopting the ammonium halide salt, and mercury adsorption sites are formed on the surface of the activated carbon through the interaction among the activated carbon, sulfur and the ammonium halide salt, so that the mercury adsorption performance of the activated carbon is further improved.
Further, the ammonium halide salt is selected from NH 4 I、NH 4 Br and NH 4 At least one of Cl.
Further, the ammonium halide salt is selected from NH 4 Br。
According to the invention, the concentration of the modifier is 0.1-5wt%.
Further, the concentration of the modifier is 0.5-1.5wt%.
According to the invention, the solid-to-liquid ratio of the activated carbon to the modifier is 10-50g/mL.
Further, the solid-to-liquid ratio of the activated carbon to the modifier is 20-30g/mL.
According to the invention, the treatment time for the modification is 2-12h.
By adjusting the concentration of the modifier, the solid-to-liquid ratio of the active carbon to the modifier and the like, the active carbon can be modified, and the damage to the pore structure of the active carbon can be effectively avoided. By adopting the technical scheme, the prepared modified activated carbon has better mercury adsorption performance; if the technological parameters described in the further preferable technical scheme of the invention are adopted, the mercury removal performance of the prepared activated carbon is further improved.
Further, the treatment time of the modification is 6-10h.
According to the invention, the activated carbon is dried.
According to the invention, the drying treatment condition is that the temperature is 40-60 ℃ and the time is 4-12h.
The fifth aspect of the invention provides the mercury-removing activated carbon prepared by the preparation method of the mercury-removing activated carbon.
The sixth aspect of the invention provides an application of the mercury removal activated carbon in the mercury removal field.
In one embodiment of the present invention, in conjunction with FIG. 1:
crushing and screening coal liquefaction residues to obtain raw material powder; the raw material powder is mixed with an adhesive and subjected to molding treatment to obtain a molded material, and the molding pressure of the molding treatment is not particularly limited in the present invention as long as the molding pressure can satisfy the preparation process of activated carbon, for example: the molding pressure is more than or equal to 10MPa; pre-oxidizing the molding material by an oxidant to obtain an oxidized material; carbonizing the oxidized material in the presence of protective atmosphere to obtain carbonized material and carbonized tail gas; and activating the carbonized material by an activating agent to obtain the activated carbon.
The active carbon can be selected according to the use condition, or the active carbon is crushed and sieved to obtain the fine active carbon.
In the following examples, various raw materials used were obtained from commercial sources without particular explanation.
Wherein the main performance parameters of the coal liquefaction residues are as follows:
the mercury penetration adsorption capacity of the coal liquefaction residue is 1.3 (120 ℃ C./(mg/g), and the specific magnetization rate is 11.20cm 3 /g。
The coal liquefaction residues are from Shenhua direct liquefaction plant, and the performance parameters are shown in table 1:
TABLE 1
In the table:
A ad ash content representing air-dried coal sample in (100%);
M ad represents the moisture content of the air-dried coal sample, and the unit is (100 percent);
V ad representing the volatile content of the air-dried coal sample, wherein the unit is (100 percent);
FC ad represents the fixed carbon content of the air-dried coal sample in units of (100%).
The following is a test method related to performance parameters in the present invention:
mercury breakthrough adsorption capacity of activated carbon is according to the standard: LY/T2707-2016 "sulfur-loaded demercuration particle activated carbon" was tested by the mercury breakthrough adsorption quantity measuring method described in the following.
The standard adopted by the industrial analysis is GB/T212-2008 "Industrial analysis method of coal".
Ash analysis used criteria: GB/T1574-2007 method for analyzing coal ash component.
Specific magnetization rate of activated carbon was tested: a vibrating sample magnetometer (PPMS-VSM, series 8600 vibrating sample magnetometer from Lake Sgore, U.S.A.) was used.
Example 1
(1) Crushing and screening the coal liquefaction residues to obtain raw material powder with the particle size of 200 meshes;
(2) Mixing 100g of the raw material powder with 15g of coal tar pitch, kneading, and forming under 15MPa to obtain a forming material;
(3) The molding material had a warp flow rate of 10Nm 3 Oxidizing agent/h (oxygen content 5vol%, balance N) 2 Gas), pre-oxidizing for 2 hours at 200 ℃ to obtain an oxidized material;
(4) From N 2 Providing a protective atmosphere, heating to 600 ℃ at room temperature at a heating rate of 5 ℃/min, and carbonizing for 1.5 hours to obtain carbonized materials and carbonized tail gas;
(5) The carbonized material uses water vapor: CO 2 ：SO 2 Is 40:30:1, the activating gas is 23vol% based on the total volume of the activating agent, and the activating gas is used as the activating agent (N is selected as the non-activating gas 2 ) At a flow rate of 200Nm 3 And under the condition of/h, heating to 900 ℃ at a heating rate of 10 ℃/min, and carrying out activation treatment on the carbonized material for 3h to obtain the activated carbon A1.
The activated carbon comprises the following components: specific magnetization of 19.39cm 3 /g。
Example 2-example 6
Activated carbon was prepared in the same manner as in example 1, and the kinds, amounts and specific preparation conditions of the respective materials used in examples 2 to 6 were as shown in Table 2, to obtain activated carbons A2 to A6.
TABLE 2
| Project | A1 | A2 | A3 | A4 | A5 | A6 |
| Raw material powder: adhesive agent | 100:15 | 100:20 | 100:30 | 100:10 | 100:15 | 100:20 |
| Oxygen content (vol%) | 5 | 5 | 10 | 10 | 10 | 10 |
| Flow rate (Nm) of oxidant 3 /h) | 10 | 10 | 10 | 10 | 10 | 10 |
| Temperature of preoxidation (. Degree. C.) | 200 | 200 | 200 | 150 | 220 | 250 |
| Time of preoxidation (h) | 2 | 1 | 2 | 2 | 2 | 2 |
| Carbonization temperature (. Degree. C.) | 550 | 650 | 600 | 500 | 580 | 600 |
| Time of charring (h) | 1.5 | 2 | 1 | 1 | 2 | 1 |
| Heating rate of carbonization (DEG C/min) | 5 | 10 | 10 | 20 | 5 | 10 |
| Water vapor: CO 2 ：SO 2 | 40:30:1 | 40:30:1 | 40:40:1 | 20:40:1 | 40:30:1 | 40:20:1 |
| Proportion of activating gas to activating agent (vol%) | 23 | 20 | 23 | 20 | 30 | 30 |
| Flow rate (Nm) of activator 3 /h) | 200 | 200 | 200 | 200 | 200 | 200 |
| Temperature of activation (. Degree. C.) | 900 | 900 | 950 | 850 | 880 | 900 |
| Time of activation (h) | 3 | 3 | 2 | 1 | 2 | 1.5 |
| Rate of temperature rise of activation (. Degree. C./min) | 10 | 10 | 10 | 10 | 5 | 10 |
Example 7
The pre-oxidation temperature was 300℃and the pre-oxidation time was 8 hours, and the same conditions as in example 1 were used to obtain activated carbon A7.
Example 8
The carbonization temperature was 400 ℃, the carbonization time was 3 hours, and the other conditions were the same as in example 1, to prepare activated carbon A8.
Example 9
Water vapor in the activated gas: CO 2 ：SO 2 Activated carbon A9 was produced at a ratio of 10:20:1 under the same conditions as in example 1.
Example 10
Activated carbon A10 was produced in the same manner as in example 1 except that the activating gas was used in an amount of 2vol% based on the total volume of the activating agent.
The activated carbon comprises the following components: specific magnetization of 14.36cm 3 /g。
Example 11
The activated carbon A11 was produced at a temperature of 1000℃under the same conditions as in example 1.
Comparative example 1
The carbonized material was not activated by an activator, and the activated carbon D1 was produced under the same conditions as in example 1.
The properties and structures of activated carbon A1-activated carbon D1 were tested and the results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the activated carbon prepared by the technical scheme of the invention has better mercury adsorption performance, and has larger specific surface area and total pore volume.
Example AX1
Grinding the activated carbon A1 obtained in example 1 into powder by a pulverizer to obtain fine activated carbon with particle diameter of 200 meshes, and adopting NH 4 The fine activated carbon is modified by the aqueous solution of Br (the concentration is 1 wt%), the solid-to-liquid ratio of the fine activated carbon to the modifier is 20g/L, and the modification time is 8h; drying the modified material at 50 ℃ for 6 hours to obtain the mercury-removing active carbon AX1.
The mercury removal activated carbon comprises the following components: specific magnetization of 18.12cm 3 /g。
The activated carbon used in the embodiment AX1 to the embodiment AX9 of the invention is fine activated carbon obtained by grinding the activated carbon into powder by a powder making machine, and the passing rate of the fine activated carbon through a 200-mesh sieve is more than 99 percent.
Examples AX2 to AX5 were prepared in a similar manner to example AX1, and the types, amounts and specific preparation conditions of the materials used were as shown in Table 4, to obtain demercuration activated carbons AX2 to AX5.
TABLE 4 Table 4
| Project | AX1 | AX2 | AX3 | AX4 | AX5 |
| Modifying agent | NH 4 Br | NH 4 I | NH 4 Cl | NH 4 Br | NH 4 Br |
| Concentration of modifier (wt%) | 1 | 0.5 | 1.5 | 3 | 5 |
| Activated carbon: modifier (g/L) | 20 | 20 | 30 | 10 | 50 |
| Treatment time for modification (h) | 8 | 8 | 8 | 10 | 12 |
| Drying treatment temperature (. Degree. C.) | 50 | 50 | 50 | 40 | 60 |
| Drying treatment time (h) | 4 | 6 | 4 | 4 | 12 |
Example AX6
The solid-to-liquid ratio of the activated carbon to the modifier was 5g/L, and the other conditions were the same as in example AX1 to obtain mercury-free activated carbon AX6.
Example AX7
The concentration of the modifier was 7wt%, the modification treatment time was 2 hours, and the other conditions were the same as in example AX1, to obtain mercury-free activated carbon AX7.
Example AX8
The drying treatment was carried out at 80℃for 1 hour, and the other conditions were the same as in example AX1 to obtain mercury-free activated carbon AX8.
Example AX9
Activated carbon a10 was used in place of activated carbon A1, and the demercuration activated carbon AX9 was obtained under the same conditions as in example AX1.
The performance and structure of the demercuration activated carbon AX 1-demercuration activated carbon AX9 were tested, and the results are shown in table 5.
TABLE 5
As can be seen from Table 5, the mercury removal activated carbon is obtained by modifying the activated carbon by the modification method of the invention, and the mercury removal performance of the mercury removal activated carbon is greatly improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. A method for preparing active carbon, which is characterized by comprising the following steps:
(1) Crushing and screening coal liquefaction residues to obtain raw material powder;
(2) Mixing the raw material powder with an adhesive, and performing molding treatment to obtain a molding material;
(3) Pre-oxidizing the molding material by an oxidant to obtain an oxidized material;
(4) Carbonizing the oxidized material in the presence of protective atmosphere to obtain carbonized material and carbonized tail gas;
(5) And activating the carbonized material by an activating agent to obtain the activated carbon.
2. The method of claim 1, wherein,
the content of fixed carbon in the coal liquefaction residues is 45-50wt% and the content of ash is 15-25wt%;
preferably, the content of iron-containing substances in the coal liquefaction residues is 0.45-1wt% and the content of sulfur-containing substances is 2-4wt%;
preferably, the particle size of the raw material powder is 120-200 meshes;
preferably, the mass ratio of the raw material powder to the binder is 100:5-20, preferably 100:10-15 parts;
preferably, the binder is selected from at least one of coal tar pitch, petroleum pitch, sulfurous acid pulp waste liquid, molasses liquid, starch liquid and carboxymethyl cellulose solution.
3. The method according to claim 1 or 2, wherein,
the oxidant is a gas mixture containing oxygen, and the content of the oxygen is less than or equal to 10vol% based on the total volume of the gas mixture;
preferably, the pre-oxidation temperature is 120-250 ℃, preferably 180-220 ℃;
preferably, the pre-oxidation time is 0.5-3 hours, preferably 1-2 hours.
4. A method according to any one of claim 1 to 3, wherein,
the carbonization temperature is 500-650 ℃, preferably 550-600 ℃;
preferably, the carbonization time is 0.5-2h, preferably 1-1.5h;
preferably, the carbonization temperature rise rate is 1-20 ℃/min, preferably 5-10 ℃/min.
5. The method according to any one of claims 1 to 4, wherein,
the activator comprises an activating gas and a non-activating gas, wherein the activating gas comprises water vapor and CO 2 And SO 2 Is a mixed gas of (1);
preferably, the water vapor in the activating gas: CO 2 ：SO 2 The volume ratio of (2) is 20-50:20-40:1, preferably 30-40:20-30:1;
preferably, the activating gas is present in an amount of 5 to 40vol%, preferably 20 to 30vol%, based on the total volume of the activator;
preferably, SO in the activator 2 And (3) burning the carbonized tail gas.
6. The method according to any one of claims 1 to 5, wherein,
the activation temperature is 750-950 ℃, preferably 850-900 ℃;
preferably, the activation time is 0.5 to 5 hours, preferably 2 to 3 hours;
preferably, the temperature rise rate of the activation is 5-10 ℃/min.
7. The method according to any one of claims 1-6, wherein,
crushing and screening the activated carbon to obtain fine activated carbon;
preferably, the particle size of the fine activated carbon is 100-400 mesh.
8. An activated carbon produced by the method of any one of claims 1-7.
9. The activated carbon of claim 8 wherein,
the specific surface area of the activated carbon is 500-1000m 2 /g; the aperture is 1.5-5nm.
10. Use of the activated carbon of claim 8 or 9 in the field of mercury removal.
11. A method for preparing mercury-removing active carbon is characterized in that,
modifying the activated carbon by using a modifier to obtain mercury-removing activated carbon;
wherein the activated carbon is the activated carbon of claim 8 or 9.
12. The method of claim 11, wherein,
the modifier is aqueous solution of ammonium halide salt;
preferably, the ammonium halide salt is selected from NH 4 I、NH 4 Br and NH 4 At least one of Cl, preferably NH 4 Br；
Preferably, the concentration of the modifier is 0.1 to 5wt%, preferably 0.5 to 1.5wt%;
preferably, the solid-to-liquid ratio of the activated carbon to the modifier is 10-50g/L, preferably 20-30g/L;
preferably, the treatment time for the modification is 2 to 12 hours, preferably 6 to 10 hours.
13. The method according to claim 11 or 12, wherein,
the method further comprises the steps of: drying the mercury removal activated carbon;
preferably, the drying treatment condition is that the temperature is 40-60 ℃ and the time is 4-12h.
14. A mercury-removing activated carbon produced by the process for producing a mercury-removing activated carbon according to any one of claims 11 to 13.
15. Use of the demercuration activated carbon according to claim 14 in the field of demercuration.
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| CN117416957B (en) * | 2023-12-19 | 2024-04-26 | 成都达奇科技股份有限公司 | Method for preparing activated carbon and activated carbon |
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