CN111675215A - Sulfur-carrying activated carbon material and preparation method and application thereof - Google Patents
Sulfur-carrying activated carbon material and preparation method and application thereof Download PDFInfo
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- CN111675215A CN111675215A CN202010599815.1A CN202010599815A CN111675215A CN 111675215 A CN111675215 A CN 111675215A CN 202010599815 A CN202010599815 A CN 202010599815A CN 111675215 A CN111675215 A CN 111675215A
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- Prior art keywords
- sulfur
- activated carbon
- carbon material
- nitrate
- metal salt
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 76
- 239000011593 sulfur Substances 0.000 claims abstract description 75
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 229910052723 transition metal Inorganic materials 0.000 claims description 39
- 239000011780 sodium chloride Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000002791 soaking Methods 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- -1 transition metal salt Chemical class 0.000 claims description 26
- 238000007792 addition Methods 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 150000003624 transition metals Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N Cobalt(II) nitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N Nickel(II) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 13
- 229940099596 manganese sulfate Drugs 0.000 claims description 13
- 239000011702 manganese sulphate Substances 0.000 claims description 13
- 235000007079 manganese sulphate Nutrition 0.000 claims description 13
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- ONDPHDOFVYQSGI-UHFFFAOYSA-N Zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L Copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L Zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 11
- 229960001763 zinc sulfate Drugs 0.000 claims description 11
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000000737 periodic Effects 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- IAAQEGBHNXAHBF-UHFFFAOYSA-N 3-thiophen-3-ylthiophene Chemical compound S1C=CC(C2=CSC=C2)=C1 IAAQEGBHNXAHBF-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L Cobalt(II) chloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L Cobalt(II) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N Copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L MANGANESE CHLORIDE Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L Nickel(II) chloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L Nickel(II) sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 229940053662 nickel sulfate Drugs 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229960000355 Copper Sulfate Drugs 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L Iron(II) sulfate Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H Iron(III) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229940032950 ferric sulfate Drugs 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052753 mercury Inorganic materials 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003610 charcoal Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000005406 washing Methods 0.000 description 19
- 229940032296 ferric chloride Drugs 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 239000003546 flue gas Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011068 load Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229940079721 Copper chloride Drugs 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000706 filtrate Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
-
- 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
- C01B32/354—After-treatment
-
- 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
Abstract
The invention relates to the field of activated carbon materials, and discloses a sulfur-carrying activated carbon material, wherein the specific surface area of the sulfur-carrying activated carbon material is 1000-2000m2The sulfur content of the sulfur-loaded activated carbon material is 10-20 wt% based on the total weight of the sulfur-loaded activated carbon material. The invention also discloses a preparation method of the sulfur-carrying activated carbon material, the sulfur-carrying activated carbon material prepared by the preparation method and application of the sulfur-carrying activated carbon material. The sulfur-carrying activated carbon material has high sulfur content, large specific surface area and good mercury adsorption effect; and the sulfur-carrying catalystThe charcoal has good stability and can prolong the service life.
Description
Technical Field
The invention relates to the field of activated carbon materials, in particular to a sulfur-carrying activated carbon material. In addition, the invention also discloses a preparation method of the sulfur-carrying activated carbon material and application of the material.
Background
Mercury is a nerve poison, has strong accumulation and irreversibility, and has great threat to human health. The coal burning and metallurgical industries are the most prominent anthropogenic mercury emissions sources. 8/16/2017 with global legal restraintThe convention about mercury water guarantee takes effect formally, and the convention stipulates that measures must be taken for coal-fired boilers and smelting flue gas to control and reduce the emission of mercury and compounds thereof in the flue gas. Mercury in flue gas exists in three forms: elemental mercury (Hg)0) Mercury (Hg) in its oxidized state2+) And particulate mercury (Hg)p). Wherein the granular mercury (Hg)p) Can be captured by a dust removal device, and oxidized mercury (Hg)2+) Is easy to dissolve in water and can be efficiently removed by a wet type flue gas purification device, and the elemental mercury (Hg) is0) Because it is extremely volatile and insoluble in water, it is difficult to directly remove by using the existing flue gas treatment device. Therefore, Hg0Becomes the key point and the difficult problem of flue gas mercury pollution treatment.
The activated carbon injection is a mature coal-fired flue gas demercuration technology at present, however, a large amount of activated carbon needs to be injected to achieve a high demercuration effect. Many researchers have introduced chemical groups (S, I, Cl, Br, etc.) with strong affinity with mercury on the surface of activated carbon to improve the mercury adsorption performance of activated carbon, wherein S can react with Hg0The reaction generates stable mercury compound (HgS), thereby effectively avoiding the secondary escape of mercury, and the research is most extensive. However, sulfur-loaded activated carbon also faces several problems: (1) the sulfur is loaded on the surface of the loaded active carbon in a weaker physical adsorption form, the thermal stability is poorer, and the sulfur can be released into flue gas in the flue gas demercuration process to bring secondary pollution; (2) generally, the more uniform the distribution of sulfur on the surface of the activated carbon, the greater the coverage, which is to Hg0The stronger the adsorption energy of (a). The common sulfur carrying method, whether the impregnation method or the coprecipitation method, can block the pore structure of the activated carbon due to the precipitation of sulfides in the sulfur carrying process, and can agglomerate on the surface of the activated carbon when the loading capacity is high, so that the loading is uneven. Conventional solutions typically produce highly dispersed sulfur-loaded activated carbon at the expense of sulfur loading, which greatly reduces its mercury adsorption capacity. The above problems limit the practical application of sulfur-loaded activated carbon.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sulfur-carrying activated carbon material, a preparation method and application thereof, wherein the sulfur-carrying activated carbon material has high sulfur content, large specific surface area and good mercury simple substance adsorption effect; and the sulfur-carrying activated carbon has better stability and better adsorption effect under the conditions of high temperature or low temperature.
In order to achieve the above object, the first aspect of the present invention provides a sulfur-loaded activated carbon material, which is 1000-2000m2The sulfur content of the sulfur-loaded activated carbon material is 10-20 wt% based on the total weight of the sulfur-loaded activated carbon material.
In a second aspect, the invention provides a preparation method of a sulfur-carrying activated carbon material, which comprises the following steps:
(1) under stirring, mixing tetrahydrofuran, a sulfur-containing solid heterocyclic organic substance, a transition metal salt and a silicon dioxide template, and removing a solvent to obtain a blocky sample, wherein the sulfur-containing solid heterocyclic organic substance is 2,2 '-bithiophene and/or 3, 3' -bithiophene; the transition metal salt is at least one selected from the group consisting of group IB metals, group IIB metals, group VIIB metals and group VIII metal salts of the periodic Table of elements;
(2) grinding the blocky sample obtained in the step (1) into powdery particles, and carbonizing the powdery particles in an inert atmosphere to obtain a carbonized product;
(3) and removing the silicon dioxide template in the carbonized product and the metal salt on the surface of the carbonized product to obtain the sulfur-carrying activated carbon material.
Preferably, in the step (1), the silica template is a hydrophilic fumed silica template, and the specific surface area of the fumed silica template is more than or equal to 200m2/g；
The transition metal salt is one or more of copper chloride, ferric chloride, zinc chloride, cobalt chloride, nickel chloride, manganese chloride, copper sulfate, ferric sulfate, zinc sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, copper nitrate, ferric nitrate, zinc nitrate, cobalt nitrate, nickel nitrate and manganese nitrate.
Further preferably, in the step (1), the addition amount of the sulfur-containing solid heterocyclic organic substance is 1 to 4g, the addition amount of the transition metal salt is 1 to 4g, and the addition amount of the silica template is 2 to 8g, based on 100mL of tetrahydrofuran;
the stirring time is 4-8 h; the solvent removal method is evaporation or freeze drying.
Preferably, in the step (2), the particle size of the powdery particles is 0.18mm-0.25 mm;
the inert atmosphere is selected from at least one of nitrogen and a gas of group zero of the periodic table of elements;
the carbonization temperature is 600-800 ℃, and the carbonization time is 2-4 h.
Preferably, in the step (3), the method for removing the silica template comprises the steps of soaking the carbonized product in an alkaline solution for 48-96 h;
the method for removing the metal salt on the surface of the carbonized product comprises the steps of soaking the carbonized product in an acid solution for 4-8 hours;
the alkali solution is sodium hydroxide solution, and the solubility of hydroxide ions in the alkali solution is 1-2 mol/L; the acid solution is sulfuric acid solution, and the solubility of hydrogen ions in the acid solution is 1-2 mol/L.
Preferably, the method further comprises: mixing the obtained sulfur-carrying activated carbon material with a transition metal salt solution under stirring, and carrying out solid-liquid separation and drying; wherein the transition metal salt is at least one selected from the group consisting of salts of metals of group IB, group IIB, group VIIB and group VIII of the periodic Table of elements.
Further preferably, the transition metal salt is one or more of copper chloride, ferric chloride, zinc chloride, cobalt chloride, nickel chloride, manganese chloride, copper sulfate, ferric sulfate, zinc sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, copper nitrate, ferric nitrate, zinc nitrate, cobalt nitrate, nickel nitrate and manganese nitrate;
the volume of the transition metal salt solution is 8-12mL calculated by 1g of the sulfur-carrying activated carbon;
the molar ratio of metal cations in the transition metal salt solution to sulfur in the sulfur-loaded activated carbon is 1-1.1: 1;
the stirring time is 2-4 h.
In a third aspect, the invention provides a sulfur-loaded activated carbon material, which is prepared according to the preparation method of the sulfur-loaded activated carbon material mentioned in any one of the above technical solutions of the second aspect.
In a fourth aspect, the invention provides an application of the sulfur-loaded activated carbon material mentioned in any one of the above first aspect and the third aspect in adsorbing elemental mercury.
Through the technical scheme, the invention has the beneficial effects that: the sulfur-carrying activated carbon material provided by the invention has higher sulfur content and specific surface area, can effectively absorb mercury simple substances in the coal-fired or metallurgical industry, and improves the safety of the coal-fired and metallurgical industry. And the sulfur of the sulfur-carrying activated carbon material is not adsorbed on the surface of carbon in a physical adsorption mode, but is connected with the carbon through a chemical bond, so that the sulfur-carrying activated carbon material has good thermal stability and has good adsorption effect under the condition of 20-170 ℃.
The preparation method provided by the invention takes the silicon dioxide as the template, and can prevent the collapse of the carbonized product in the carbonization process so as to improve the specific surface area of the carbonized product. Compared with the traditional loading method, the method takes the sulfur-containing solid heterocyclic organic matter as a reactant, sulfur is not loaded on the surface of carbon in a physical adsorption mode, but is connected with the carbon in a chemical bond mode, and the thermal stability is higher. Based on the principle of strong bonding interaction between transition metal and sulfur (according to the theory of soft and hard acids and bases, the transition metal and the sulfur belong to soft acid and soft base respectively, so that strong covalent bonds can be formed between the transition metal and the soft base), the high-load and high-dispersion transition metal sulfide loaded activated carbon is prepared.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a sulfur-loaded activated carbon material, wherein the specific surface area of the sulfur-loaded activated carbon material is 1000-2The sulfur content of the sulfur-loaded activated carbon material is 10-20 wt% based on the total weight of the sulfur-loaded activated carbon material.
In a second aspect, the invention provides a preparation method of a sulfur-carrying activated carbon material, which comprises the following steps:
(1) under stirring, mixing tetrahydrofuran, a sulfur-containing solid heterocyclic organic substance, a transition metal salt and a silicon dioxide template, and removing a solvent to obtain a blocky sample, wherein the sulfur-containing solid heterocyclic organic substance is 2,2 '-bithiophene and/or 3, 3' -bithiophene; the transition metal salt is at least one selected from the group consisting of group IB metals, group IIB metals, group VIIB metals and group VIII metal salts of the periodic Table of elements;
(2) grinding the blocky sample obtained in the step (1) into powdery particles, and carbonizing the powdery particles in an inert atmosphere to obtain a carbonized product;
(3) and removing the silicon dioxide template in the carbonized product and the metal salt on the surface of the carbonized product to obtain the sulfur-carrying activated carbon material.
The silicon dioxide template can adopt a common silicon dioxide template, preferably a hydrophilic gas-phase silicon dioxide template, the surface area of the sulfur-carrying activated carbon prepared by using the hydrophilic gas-phase silicon dioxide template is larger, and the adsorption efficiency of the sulfur-carrying activated carbon can be effectively improved. And moreover, the modified starch has no toxicity, no smell and no pollution, has good chemical inertness, special thixotropic property and good hydrophilic property, and can react with reactants more fully. Wherein the specific surface area of the hydrophilic fumed silica template is more than or equal to 200m2/g。
The transition metal salt may be at least one of copper chloride, ferric chloride, zinc chloride, cobalt chloride, nickel chloride, manganese chloride, copper sulfate, iron sulfate, zinc sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, copper nitrate, ferric nitrate, zinc nitrate, cobalt nitrate, nickel nitrate, and manganese nitrate. Cobalt nitrate is preferred. Preferably, the addition amount of the sulfur-containing solid heterocyclic organic substance is 1-4g, the addition amount of the transition metal salt is 1-4g, and the addition amount of the silica template is 2-8g, calculated by 100mL of tetrahydrofuran.
In the step (1), the stirring is performed to fully react the tetrahydrofuran, the sulfur-containing solid heterocyclic organic compound, the transition metal salt and the silica template, and the stirring time may be determined according to the specific degree of the reaction, and preferably, the stirring time is 4 to 8 hours. The solvent removing method can adopt a conventional technical means to remove the solvent, and preferably adopts evaporation or freeze drying, and the evaporation can adopt common evaporation or rotary evaporation, preferably adopts rotary evaporation, so that the evaporation time is reduced, and the evaporation efficiency is improved.
In the step (2), the particle size of the powdery particles obtained after grinding is preferably 0.18mm to 0.25 m. The inert atmosphere is at least one selected from nitrogen and gases of the zero group of the periodic table of elements, preferably nitrogen and/or helium, more preferably nitrogen, so that oxidation in the carbonization process can be prevented, and the preparation cost can be reduced. The carbonization temperature is 600-800 ℃, and the carbonization time is 2-4 h.
In the step (3), the step of removing the silica template and the step of removing the metal salt on the surface of the carbonized product are not in sequence, and the step of removing the carbon dioxide template may be performed first, or the step of removing the metal salt on the surface of the carbonized product may be performed first, but the steps are all washed with clean water. The method for removing the silicon dioxide template comprises the steps of placing the carbonized product in an alkaline solution for soaking for 48-96 h; the method for removing the metal salt on the surface of the carbonized product is to put the carbonized product into an acid solution for soaking for 4-8 h. The alkali solution can adopt a conventional alkali solution, such as a potassium hydroxide and/or sodium hydroxide solution, and preferably a sodium hydroxide solution; the acid solution may be a conventional acid solution, such as a hydrochloric acid solution and/or a sulfuric acid solution, preferably a sulfuric acid solution. Further preferably, the hydroxide ion solubility in the alkali solution is 1-2 mol/L; the solubility of hydrogen ions in the acid solution is 1-2 mol/L.
In order to increase the content of transition metals in the sulfur-loaded activated carbon, the method further comprises: mixing the obtained sulfur-carrying activated carbon material with a transition metal salt solution under stirring, and carrying out solid-liquid separation and drying; wherein the transition metal salt is at least one selected from the group consisting of salts of metals of group IB, group IIB, group VIIB and group VIII of the periodic Table of elements.
The solid-liquid separation can adopt a conventional solid-liquid separation method, such as: centrifugation, precipitation, filtration and the like, preferably adopts a filtration method, is simple and convenient, and has better separation effect. The stirring time may be 2-4 h.
The transition metal salt may be at least one of copper chloride, ferric chloride, zinc chloride, cobalt chloride, nickel chloride, manganese chloride, copper sulfate, iron sulfate, zinc sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, copper nitrate, ferric nitrate, zinc nitrate, cobalt nitrate, nickel nitrate, and manganese nitrate.
Preferably, the volume of the transition metal salt solution is 8-12mL based on 1g of the sulfur-loaded activated carbon, and the volume of the transition metal salt solution may be 8mL, 9mL, 10mL, 11mL, 12mL, or any value between these values. More preferably, the molar ratio of the metal cation in the transition metal salt solution to the sulfur element in the sulfur-loaded activated carbon is 1-1.1: 1.
In a third aspect, the invention provides a sulfur-loaded activated carbon material, which is prepared according to the preparation method of the sulfur-loaded activated carbon material mentioned in any one of the above technical solutions of the second aspect.
In a fourth aspect, the invention provides an application of the sulfur-loaded activated carbon material mentioned in any one of the above first aspect and the third aspect in adsorbing elemental mercury.
The present invention will be described in detail below by way of examples.
In the examples below, the sulphur content is determined by the national standard GB/T214-1996; the specific surface area is measured by the BET method; the adsorption amount of the mercury simple substance is measured by a gold film enrichment/cold atomic absorption spectrophotometry method (HJ 910-2017).
Tetrahydrofuran was purchased from Shanghai Merlin under the product designation T818767; 2, 2' -bithiophene is available from Shanghai Michelin under the product designation B801836; 3, 3' -bithiophene is available from Shanghai Michelin under the product designation AK-72774; cobalt nitrate, copper chloride, zinc sulfate, ferric chloride, manganese sulfate and nickel nitrate are all purchased from national medicine group chemical reagent limited, and the product labels are L03641801. XW74473943, 51028361, 810152291, 53204662, 1001431933; the hydrophilic fumed silica template is available from Shanghai Michelin and has a specific surface area of 200m2(ii)/g; the silica was purchased from Shanghai Michelin, having a particle size of 10 μm and a specific surface area of 120m2/g。
The BET specific surface area analyzer is available from Beschard instruments technologies, Inc. and is 3H-2000 BET-A.
Example 1
(1) Mixing 100mL of tetrahydrofuran, 2.5g of 2, 2' -bithiophene, 2.5g of cobalt nitrate and 4g of hydrophilic fumed silica template, stirring for 3 hours, and freeze-drying to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 70-mesh screen, and then carbonizing in a nitrogen atmosphere at 700 ℃ for 3 hours to obtain a carbonized product;
(3) soaking the carbonized product in 1.5mol/L sodium hydroxide solution for 72h, washing with water, then soaking the carbonized product in 0.8mol/L sulfuric acid solution for 6h, and washing with water to obtain an initial sulfur-carrying activated carbon material;
(4) and (3) soaking the initial sulfur-loaded activated carbon material in a cobalt nitrate solution (the addition amount of cobalt nitrate is 0.03mol) for 3h according to the mass-to-volume ratio of 1:10(g/mL) to obtain the sulfur-loaded activated carbon material.
Example 2
(1) Mixing 100mL of tetrahydrofuran, 1g of 3, 3' -bithiophene, 0.5g of copper chloride, 0.5g of zinc sulfate and 2g of hydrophilic fumed silica template, stirring for 2 hours, and performing rotary evaporation to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 60-mesh screen, and then carbonizing in a helium atmosphere at 600 ℃ for 4 hours to obtain a carbonized product;
(3) soaking the carbonized product in 0.5mol/L sulfuric acid solution for 8 hours, washing with water, then soaking the carbonized product in 1mol/L sodium hydroxide solution for 96 hours, and washing with water to obtain an initial sulfur-carrying activated carbon material;
(4) placing the initial sulfur-carrying activated carbon material into a transition metal salt solution (the addition amount of copper chloride is 0.006mol, and the addition amount of zinc sulfate is 0.006mol) according to the mass-to-volume ratio of 1:8(g/mL) for soaking for 3h to obtain the sulfur-carrying activated carbon material.
Example 3
(1) Mixing 100mL of tetrahydrofuran, 4g of 2, 2' -bithiophene, 1g of ferric chloride, 1g of manganese sulfate, 2g of nickel nitrate and 8g of hydrophilic fumed silica template, stirring for 3 hours, and performing rotary evaporation to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 80-mesh screen, and then carbonizing in a nitrogen atmosphere at 800 ℃ for 2 hours to obtain a carbonized product;
(3) soaking the carbonized product in 2mol/L sodium hydroxide solution for 48h, washing with water, then soaking the carbonized product in 1mol/L sulfuric acid solution for 4h, and washing with water to obtain an initial sulfur-carrying activated carbon material;
(4) placing the initial sulfur-carrying activated carbon material into a transition metal salt solution (the addition amount of ferric chloride is 0.012mol, the addition amount of manganese sulfate is 0.012mol, and the addition amount of nickel nitrate is 0.01mol) according to the mass-to-volume ratio of 1:10(g/mL) for soaking for 3h to obtain the sulfur-carrying activated carbon material.
Example 4
(1) Mixing 100mL of tetrahydrofuran, 2.5g of 2, 2' -bithiophene, 2.5g of cobalt nitrate and 4g of silicon dioxide template, stirring for 3 hours, and freeze-drying to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 70-mesh screen, and then carbonizing in a nitrogen atmosphere at 700 ℃ for 3 hours to obtain a carbonized product;
(3) soaking the carbonized product in 1.5mol/L sodium hydroxide solution for 72h, washing with water, then soaking the carbonized product in 0.8mol/L sulfuric acid solution for 6h, and washing with water to obtain an initial sulfur-carrying activated carbon material;
(4) and (3) soaking the initial sulfur-loaded activated carbon material in a cobalt nitrate solution (the addition amount of cobalt nitrate is 0.03mol) for 3h according to the mass-to-volume ratio of 1:10(g/mL) to obtain the sulfur-loaded activated carbon material.
Example 5
(1) Mixing 100mL of tetrahydrofuran, 4g of 2, 2' -bithiophene, 1g of ferric chloride, 1g of manganese sulfate, 2g of nickel nitrate and 8g of hydrophilic fumed silica template, stirring for 3 hours, and performing rotary evaporation to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 80-mesh screen, and then carbonizing in a nitrogen atmosphere at 800 ℃ for 2 hours to obtain a carbonized product;
(3) soaking the carbonized product in 2mol/L potassium hydroxide solution for 48h, washing with water, then soaking the carbonized product in 1mol/L hydrochloric acid solution for 4h, and washing with water to obtain an initial sulfur-loaded activated carbon material;
(4) placing the initial sulfur-carrying activated carbon material into a transition metal salt solution (the addition amount of ferric chloride is 0.012mol, the addition amount of manganese sulfate is 0.012mol, and the addition amount of nickel nitrate is 0.01mol) according to the mass-to-volume ratio of 1:10(g/mL) for soaking for 3h to obtain the sulfur-carrying activated carbon material.
Example 6
(1) Mixing 100mL of tetrahydrofuran, 2.5g of 2, 2' -bithiophene, 2.5g of cobalt nitrate and 4g of hydrophilic fumed silica template, stirring for 3 hours, and freeze-drying to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 70-mesh screen, and then carbonizing in a nitrogen atmosphere at 700 ℃ for 3 hours to obtain a carbonized product;
(3) and (3) placing the carbonized product in 1.5mol/L sodium hydroxide solution for soaking for 72h, washing with water, then placing the carbonized product in 0.8mol/L sulfuric acid solution for soaking for 6h, and washing with water to obtain the initial sulfur-carrying activated carbon material.
Example 7
(1) Mixing 100mL of tetrahydrofuran, 1g of 3, 3' -bithiophene, 0.5g of copper chloride, 0.5g of zinc sulfate and 2g of hydrophilic fumed silica template, stirring for 2 hours, and performing rotary evaporation to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 60-mesh screen, and then carbonizing in a helium atmosphere at 500 ℃ for 4 hours to obtain a carbonized product;
(3) soaking the carbonized product in 0.5mol/L sulfuric acid solution for 8 hours, washing with water, then soaking the carbonized product in 1mol/L sodium hydroxide solution for 96 hours, and washing with water to obtain an initial sulfur-carrying activated carbon material;
(4) placing the initial sulfur-carrying activated carbon material into a transition metal salt solution (the addition amount of copper chloride is 0.006mol, and the addition amount of zinc sulfate is 0.006mol) according to the mass-to-volume ratio of 1:8(g/mL) for soaking for 3h to obtain the sulfur-carrying activated carbon material.
Example 8
(1) Mixing 100mL of tetrahydrofuran, 4g of 2, 2' -bithiophene, 1g of ferric chloride, 1g of manganese sulfate, 2g of nickel nitrate and 8g of hydrophilic fumed silica template, stirring for 3 hours, and performing rotary evaporation to remove a solvent to obtain a block sample;
(2) grinding the block sample obtained in the step (1) into powdery particles, screening by using a 80-mesh screen, and then carbonizing in a nitrogen atmosphere at 900 ℃ for 2 hours to obtain a carbonized product;
(3) soaking the carbonized product in 2mol/L sodium hydroxide solution for 48h, washing with water, then soaking the carbonized product in 1mol/L sulfuric acid solution for 4h, and washing with water to obtain an initial sulfur-carrying activated carbon material;
(4) placing the initial sulfur-carrying activated carbon material into a transition metal salt solution (the addition amount of ferric chloride is 0.012mol, the addition amount of manganese sulfate is 0.012mol, and the addition amount of nickel nitrate is 0.01mol) according to the mass-to-volume ratio of 1:10(g/mL) for soaking for 3h to obtain the sulfur-carrying activated carbon material.
Comparative example
(1) Dissolving 2g of thiophene in 200mL of acetonitrile solvent, slowly adding the thiophene into 100mL of acetonitrile solution dissolved with 20g of ferric chloride, quickly stirring for 20h at normal temperature, washing with acetone and acetonitrile until the filtrate is colorless, and drying in vacuum at 50 ℃ for 30h to obtain polythiophene for later use.
(2) Mixing polythiophene and potassium hydroxide according to the mass ratio of 1:2, and carbonizing at 800 ℃ for 1h in a nitrogen atmosphere. Washing the carbonized sample with 5 wt% hydrochloric acid, washing with distilled water until the supernatant is neutral, and drying at 100 deg.C for 30h to obtain sulfur-carrying activated carbon material.
The sulfur content measurements, BET measurements, and mercury adsorption measurements at various temperatures were performed on the sulfur-loaded activated carbon materials obtained in examples 1-8 and comparative examples above to obtain the following data:
as can be seen from the data of examples 1 to 8 and comparative examples, the sulfur-loaded activated carbon material can achieve a mercury adsorption amount of 20 to 32mg/g, which is 2 to 3 times that of the sulfur-loaded activated carbon material of the comparative example, and further, the sulfur-loaded activated carbon material has excellent thermal stability and exhibits excellent mercury adsorption performance at a temperature range of 20 to 170 ℃ as compared with the sulfur-loaded activated carbon obtained in the comparative example.
Comparing the data of example 1 and example 4, it can be seen that the specific surface area of the obtained sulfur-loaded activated carbon material is larger and the adsorption performance of the sulfur-loaded activated carbon material to the mercury simple substance is better by selecting the hydrophilic fumed silica.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The sulfur-carrying activated carbon material is characterized in that the specific surface area of the sulfur-carrying activated carbon material is 1000-2000m2The sulfur content of the sulfur-loaded activated carbon material is 10-20 wt% based on the total weight of the sulfur-loaded activated carbon material.
2. A preparation method of a sulfur-carrying activated carbon material is characterized by comprising the following steps:
(1) under stirring, mixing tetrahydrofuran, a sulfur-containing solid heterocyclic organic substance, a transition metal salt and a silicon dioxide template, and removing a solvent to obtain a blocky sample, wherein the sulfur-containing solid heterocyclic organic substance is 2,2 '-bithiophene and/or 3, 3' -bithiophene; the transition metal salt is at least one selected from the group consisting of group IB metals, group IIB metals, group VIIB metals and group VIII metal salts of the periodic Table of elements;
(2) grinding the blocky sample obtained in the step (1) into powdery particles, and carbonizing the powdery particles in an inert atmosphere to obtain a carbonized product;
(3) and removing the silicon dioxide template in the carbonized product and the metal salt on the surface of the carbonized product to obtain the sulfur-carrying activated carbon material.
3. The method for preparing the sulfur-loaded activated carbon material according to claim 2, wherein in the step (1), the silica template is a hydrophilic fumed silica template, and the specific surface area of the fumed silica template is not less than 200m2/g；
The transition metal salt is one or more of copper chloride, ferric chloride, zinc chloride, cobalt chloride, nickel chloride, manganese chloride, copper sulfate, ferric sulfate, zinc sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, copper nitrate, ferric nitrate, zinc nitrate, cobalt nitrate, nickel nitrate and manganese nitrate.
4. The preparation method of the sulfur-carrying activated carbon material according to claim 3, wherein in the step (1), the addition amount of the sulfur-containing solid heterocyclic organic substance is 1 to 4g, the addition amount of the transition metal salt is 1 to 4g, and the addition amount of the silica template is 2 to 8g, based on 100mL of tetrahydrofuran;
the stirring time is 4-8 h; the solvent removal method is evaporation or freeze drying.
5. The method for preparing a sulfur-loaded activated carbon material as claimed in claim 2, wherein in the step (2), the particle size of the powdery particles is 0.18mm to 0.25 mm;
the inert atmosphere is selected from at least one of nitrogen and a gas of group zero of the periodic table of elements;
the carbonization temperature is 600-800 ℃, and the carbonization time is 2-4 h.
6. The method for preparing a sulfur-loaded activated carbon material according to claim 2, wherein in the step (3), the method for removing the silica template comprises the steps of soaking the carbonized product in an alkaline solution for 48 to 96 hours;
the method for removing the metal salt on the surface of the carbonized product comprises the steps of soaking the carbonized product in an acid solution for 4-8 hours;
the alkali solution is sodium hydroxide solution, and the solubility of hydroxide ions in the alkali solution is 1-2 mol/L; the acid solution is sulfuric acid solution, and the solubility of hydrogen ions in the acid solution is 1-2 mol/L.
7. The method for producing a sulfur-carrying activated carbon material according to any one of claims 2 to 6, further comprising: mixing the obtained sulfur-carrying activated carbon material with a transition metal salt solution under stirring, and carrying out solid-liquid separation and drying; wherein the transition metal salt is at least one selected from the group consisting of salts of metals of group IB, group IIB, group VIIB and group VIII of the periodic Table of elements.
8. The method for preparing a sulfur-carrying activated carbon material according to claim 7, wherein the transition metal salt is one or more of copper chloride, iron chloride, zinc chloride, cobalt chloride, nickel chloride, manganese chloride, copper sulfate, iron sulfate, zinc sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, copper nitrate, iron nitrate, zinc nitrate, cobalt nitrate, nickel nitrate, and manganese nitrate;
the volume of the transition metal salt solution is 8-12mL calculated by 1g of the sulfur-carrying activated carbon;
the molar ratio of metal cations in the transition metal salt solution to sulfur in the sulfur-loaded activated carbon is 1-1.1: 1;
the stirring time is 2-4 h.
9. A sulfur-loaded activated carbon material, characterized in that it is prepared according to the method for preparing a sulfur-loaded activated carbon material according to any one of claims 2 to 8.
10. Use of a sulfur-loaded activated carbon material according to claim 1 or claim 9 for adsorbing elemental mercury.
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