CN115400719B - High-sulfur high-humidity flue gas mercury removal self-sustaining activated adsorbent and preparation and regeneration methods thereof - Google Patents
High-sulfur high-humidity flue gas mercury removal self-sustaining activated adsorbent and preparation and regeneration methods thereof Download PDFInfo
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- CN115400719B CN115400719B CN202211121674.8A CN202211121674A CN115400719B CN 115400719 B CN115400719 B CN 115400719B CN 202211121674 A CN202211121674 A CN 202211121674A CN 115400719 B CN115400719 B CN 115400719B
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 111
- 239000003463 adsorbent Substances 0.000 title claims abstract description 106
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 75
- 239000011593 sulfur Substances 0.000 title claims abstract description 75
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003546 flue gas Substances 0.000 title claims abstract description 49
- 238000011069 regeneration method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 49
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000004913 activation Effects 0.000 claims abstract description 25
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 13
- -1 transition metal salt Chemical class 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 5
- 230000006698 induction Effects 0.000 claims abstract description 4
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 238000000352 supercritical drying Methods 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 21
- 230000001172 regenerating effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 238000007323 disproportionation reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002594 sorbent Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000002912 waste gas Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000007420 reactivation Effects 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 abstract description 4
- 238000007493 shaping process Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 150000002730 mercury Chemical class 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 3
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229940079101 sodium sulfide Drugs 0.000 description 2
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- LRWQWQFSOAMWKT-UHFFFAOYSA-N [Cd].[Mo] Chemical compound [Cd].[Mo] LRWQWQFSOAMWKT-UHFFFAOYSA-N 0.000 description 1
- ARLTWUYDMLJBOX-UHFFFAOYSA-N [Mo]=S.[Zn] Chemical compound [Mo]=S.[Zn] ARLTWUYDMLJBOX-UHFFFAOYSA-N 0.000 description 1
- LHFIRYRWRKKZFC-UHFFFAOYSA-N [S].[Mo].[Cd] Chemical compound [S].[Mo].[Cd] LHFIRYRWRKKZFC-UHFFFAOYSA-N 0.000 description 1
- WJPZDRIJJYYRAH-UHFFFAOYSA-N [Zn].[Mo] Chemical compound [Zn].[Mo] WJPZDRIJJYYRAH-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- OIGPMFVSGDDYHS-UHFFFAOYSA-N copper sulfanylidenemolybdenum Chemical compound [S].[Cu].[Mo] OIGPMFVSGDDYHS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a self-sustaining activated adsorbent for removing mercury from high-sulfur high-humidity flue gas and a preparation and regeneration method thereof, wherein the self-sustaining activated adsorbent is a metal sulfide composed of transition metal elements and sulfur elements, and the preparation method comprises the following specific steps: the precursor is selected from transition metal salt and sulfur source, and a metal sulfide adsorbent is synthesized by a precipitation method or a hydrothermal method; shaping the metal sulfide type adsorbent by supercritical drying or freeze drying to expose sulfur sites on the surface of the metal sulfide type adsorbent; activating sulfur sites on the surface of the metal sulfide adsorbent through solid-liquid phase ion exchange; the regeneration method comprises the following specific steps: the sulfur dioxide reacts with the surface of the metal sulfide adsorbent to generate new active sites under the induction of transition metal ions, so that the sulfur site reconstruction and the self-sustained activation effect are realized. Compared with the prior art, the method has the advantages of high zero-valent mercury removal efficiency, resistance to high-concentration sulfur dioxide, self-sustained activation of the adsorbent and the like.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a self-sustaining activated adsorbent for removing mercury from high-sulfur high-humidity flue gas and a preparation and regeneration method thereof.
Background
Mercury has the characteristics of high toxicity, easy migration and transformation, bioaccumulation and the like in the environment, and is a heavy metal element with extremely high harm. China is considered as the largest mercury discharge country, and the problem of local and regional pollution is prominent and the international society is highly concerned. Therefore, china has been specially put out of the ' twelve five ' plan for comprehensive prevention and treatment of heavy metal pollution ', aims to strengthen the control of mercury and other heavy metal pollution, and formally becomes the contracted state of the international ' water with mercury convention ' in 2016, and is responsible for huge mercury emission reduction pressure.
For high-mercury flue gas generated by nonferrous metal smelting, not only removal of mercury from the flue gas, but also enrichment and recovery of mercury are considered. Because the flue gas is mostly accompanied with high-concentration sulfur dioxide, a two-to-two-suction process is generally adopted to convert the sulfur dioxide into sulfuric acid. Before acid production, the flue gas is pretreated by adopting a cooling and washing method to wash out other impurities in the flue gas, so that the influence of the impurities on the performance of a sulfur dioxide conversion catalyst and the quality of sulfuric acid is avoided. But due to zero-valent mercury (Hg) 0 ) The low solubility and high volatility of the product are easy to enter the acid making smoke, and the quality of the sulfuric acid product is reduced.
Patent CN 109092277A discloses a method for activating and regenerating a metal sulfide mercury removal adsorbent by moderately soaking a metal sulfide body in an activating solution composed of a cupric salt solution, followed by separation, washing, and drying, to complete the activation of the adsorbent, which is then used to adsorb mercury in a gas stream. When the adsorbent is deactivated due to saturation of adsorption of mercury, the adsorbed mercury is released by heat treatment, and the resource is recovered. And (5) soaking the adsorbent subjected to heat treatment in an activating solution again to finish the regeneration of the metal sulfide. However, the adsorbent prepared by the method still needs to be independently regenerated after being taken out, which is unfavorable for continuous production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a self-sustained activation adsorbent for removing mercury from high-sulfur and high-humidity flue gas and a preparation and regeneration method thereof.
The aim of the invention can be achieved by the following technical scheme:
a self-sustaining activated adsorbent for removing mercury from high-sulfur high-humidity fume is composed of simple metal sulfide or coordination metal sulfide composed of two or more transition metal elements and sulfur elements.
Further, the transition metal element comprises ds zone elements which are one or more selected from copper, zinc, silver, cadmium and mercury, and the ds zone elements also belong to sulfur-philic elements and are easy to form metal sulfides with sulfur elements, so that the generation and activation of the self-sustained activation adsorbent surface nascent sulfur are facilitated.
The preparation method of the self-sustaining activated adsorbent for removing mercury from high-sulfur high-humidity flue gas comprises the following steps:
s11, selecting transition metal salt and a sulfur source as precursors, and synthesizing a metal sulfide adsorbent by a precipitation method or a hydrothermal method;
and S12, forming the metal sulfide adsorbent in a post-treatment mode, so as to realize high exposure and activation treatment of sulfur sites on the surface of the metal sulfide adsorbent, and obtain the self-sustaining activated adsorbent for removing mercury.
Further, in the step S11, the transition metal salt is selected from one or more of chloride, sulfate, nitrate and acetate, the sulfur source is selected from one or more of elemental sulfur, sodium sulfide, thioacetamide and thiourea, and the molar ratio of the transition metal element in the transition metal salt to the sulfur element in the sulfur source is 1 (0.5-1.5);
the reaction temperature of the precipitation method is room temperature, and the reaction time is 0.5-6h;
the reaction temperature of the hydrothermal method is 120-180 ℃ and the reaction time is 6-12h.
Further, the specific steps of the post-processing method in step S12 are as follows: high exposure of sulfur sites is achieved by supercritical drying, freeze drying or vacuum drying; the activation of sulfur sites is realized by utilizing the solubility difference among different sulfides through solid-liquid phase ion exchange, such as soaking for 2-20min through 0.01-0.10mol/L copper sulfate or copper nitrate solution, and the sulfur sites on the surface of the metal sulfide type adsorbent are activated.
A regeneration method of a self-sustaining activated adsorbent for removing mercury from high-sulfur high-humidity flue gas, which comprises the following steps:
s21, the self-sustaining activated adsorbent is used for treating high-sulfur high-humidity flue gas, and by utilizing the characteristics of the high-sulfur high-humidity flue gas, sulfur dioxide gas and low-valence sulfur species on the surface of the self-sustaining activated adsorbent are subjected to inverse disproportionation reaction to form a sulfur etching effect, and generated nascent sulfur forms a new active site under the induction of transition metal ions, so that site reconstruction and self-sustaining activation effects are realized;
s22, when the consumption of low-valence sulfur on the surface of the self-sustained activated adsorbent is lower than 50% or the adsorption efficiency of mercury is lower than 50%, intermittently adding hydrogen sulfide gas into the flue gas from the upstream of the adsorption device, and adsorbing the hydrogen sulfide gas by the self-sustained activated adsorbent and supplementing the low-valence sulfur on the surface of the self-sustained activated adsorbent when the hydrogen sulfide gas passes through the adsorbent layer, so that the self-sustained activated adsorbent performance is recovered, and the self-sustained activated adsorbent can be recycled;
s23, when the mercury adsorption concentration on the self-sustained activated adsorbent is higher than 100g/kg, taking out, collecting and recycling the regenerated mercury by using a heating regeneration and condensation method, and recycling the regenerated self-sustained activated adsorbent after reactivation of hydrogen sulfide gas.
The self-sustaining activation effect means that under the condition of wet flue gas, high-concentration sulfur dioxide can be subjected to inverse disproportionation reaction with sulfur sites (comprising sulfur ions dissolved out by the mercury removal material and auxiliary trace (10-200 ppm) hydrogen sulfide gas) at the wet interface of the adsorption material, so that active sites are continuously generated, and high-capacity adsorption, enrichment and recovery of mercury are realized.
Further, the high-sulfur high-humidity flue gas in the step S21 is mercury-containing and oxysulfide-containing waste gas generated by the nonferrous metal smelting industry, the temperature after wet washing is 20-80 ℃, and the relative humidity is 60-95%; the mercury in the high-sulfur high-humidity flue gas after wet washing mainly exists in the form of zero-valent mercury with the concentration of 0.05-50mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of sulfur dioxide gas is 0.2-10%;
the low-valence sulfur includes sulfur ions that are eluted from the self-sustaining activated sorbent interface itself.
Further, the self-sustaining activated adsorbent in the step S21 is used for treating the high-sulfur and high-humidity flue gas in a fixed bed or moving bed mode, and the space velocity (the volume of gas which can be treated in one hour per cubic meter of adsorbent) used in the treatment is 1000-20000h -1 。
Further, the concentration of the hydrogen sulfide gas in step S22 is 10 to 200ppm.
Further, the specific steps of the heating regeneration and condensation method in step S23 are as follows: heating the self-sustaining activated adsorbent to 250-350 ℃ under the protection of nitrogen to obtain high-concentration zero-valent mercury gas, condensing and adsorbing to recover zero-valent mercury products; the regenerated self-sustaining activated adsorbent is cooled and then activated for 5-30min by hydrogen sulfide gas with the concentration of 10-200ppm.
Compared with the prior art, the invention has the following advantages:
(1) The self-sustaining activated adsorbent can avoid sulfation of the self-sustaining activated adsorbent due to low-valence sulfur, so that the interference of high-concentration sulfur dioxide is resisted, the high-capacity trapping of the flue gas mercury is realized, and the secondary pollution problems such as cross-medium transfer of zero-valence mercury are avoided;
(2) The self-sustaining activation effect of the invention can fully utilize the characteristics of the flue gas to realize the in-situ sustaining activation of the adsorbent;
(3) After the self-sustaining activated adsorbent is used, mercury resources can be recovered through high-temperature regeneration, and the self-sustaining activated adsorbent can be recycled after secondary activation.
Drawings
Fig. 1 is a schematic diagram of the mercury removal process and self-sustaining activation and mercury adsorption principle of embodiment 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The effect of the self-sustaining activated adsorbent of the present invention will be further described below by taking nitrogen, which is a mixed background gas of zero-valent mercury, sulfur dioxide and water vapor, as an example of simulated flue gas.
Example 1
The preparation, mercury adsorption, mercury recovery and cyclic regeneration of the copper sulfide-based self-sustained activated mercury removal adsorbent comprise the following steps:
(1) Respectively weighing 0.1mol of sodium sulfide nonahydrate and 0.1mol of copper nitrate, adding 50mL of deionized water for dissolution, slowly dropwise adding the copper nitrate solution into the sodium sulfide solution, and stirring for 30min;
(2) After the reaction is finished, centrifugally separating copper sulfide black precipitate, and vacuum drying at 60 ℃ for 12 hours to obtain the copper sulfide-based self-sustaining activated mercury removal adsorbent;
(3) Weighing 30mg of adsorbent in a 6mm quartz reaction tube, wherein the zero-valent mercury concentration in simulated flue gas input by an inlet is 1.8mg/m 3 The total flow is 500mL/min, the reaction temperature is 80 ℃, the initial mercury adsorption efficiency reaches 100%, and the reaction temperature is reduced to 78% after 300min;
(4) After 5000ppm sulfur dioxide and 5% water vapor are further introduced, the mercury removal efficiency is rapidly improved to 95%, and the stable mercury removal efficiency is maintained for more than 300min;
(5) The adsorbent is desorbed through temperature programming (50-350 ℃ and 5 ℃/min) under the protection of nitrogen, zero-valent mercury is separated from the surface of the adsorbent again, the desorption peak temperature is 200-250 ℃, and the mercury recovery rate is 96.7%;
(6) The mercury adsorption experiment is carried out again on the copper sulfide-based mercury removal adsorbent after mercury recovery, and zero-valent mercury concentration in imported simulated flue gas is calculated1.8mg/m 3 The total flow is 500mL/min, the reaction temperature is 80 ℃, the initial mercury adsorption efficiency reaches 15%, and the reaction time is reduced to 5% after 30min;
(7) Adding 20mL of 0.05mol/L copper sulfate solution into the desorbed copper sulfide-based mercury removal adsorbent again, performing ultrasonic activation for 2min, performing centrifugal separation, and performing vacuum drying at 60 ℃ for 12h to obtain a regenerated copper sulfide-based self-sustaining activated mercury removal adsorbent;
(8) The 3h mercury removal efficiencies of the adsorbents after the first wheel, the second wheel, the third wheel and the fourth wheel are respectively 98.5%, 97.9%, 99.2% and 98.2%, and the cycle performance is good.
Fig. 1 is a schematic diagram of the mercury removal process and self-sustaining activation and mercury adsorption principle of embodiment 1 of the present invention. As shown in fig. 1, after the nonferrous smelting flue gas is subjected to upstream wet washing treatment and temperature reduction, the zero-valent mercury is efficiently adsorbed by using an adsorbent with self-sustained activation adsorption performance in a flue gas environment, and high-capacity enrichment is realized. The adsorbent consists of specific metal sulfide, and in the use process, sulfur dioxide and partial low-valence sulfur species on the surface of the adsorbent are subjected to inverse disproportionation to form an etching effect, so that nascent elemental sulfur is generated, and then site reconstruction is realized by forming new adsorption active sites through the induction of transition metal ions on the surface of the sulfide, so that the adsorption and activation performances of the adsorbent are ensured, and the capacity is greatly improved compared with that of a conventional adsorbent. The transition metal ions have surface migration effect, so that the process of sulfur etching, activation and mercury adsorption is continuously and circularly carried out. When low-valence sulfur species on the surface of the adsorbent are gradually consumed to a certain extent, the adsorbent is subjected to intermittent in-situ vulcanization treatment by utilizing hydrogen sulfide gas with a certain concentration, and the self-sustained activation performance of the adsorbent is recovered, so that the high-capacity adsorption of mercury on the adsorbent is realized.
Example 2
The preparation of the copper-molybdenum bimetal coordination sulfide self-sustaining activated mercury removal adsorbent and mercury adsorption comprise the following steps:
(1) Respectively weighing 0.1mol of ammonium tetrathiomolybdate and 0.1mol of copper chloride, adding 50mL of deionized water for dissolution, slowly dropwise adding the copper chloride solution into the ammonium tetrathiomolybdate solution, stirring for 3 hours, and centrifuging to separate precipitate;
(2) Freezing at-80 ℃ for 6 hours, and freeze-drying at-50 ℃ for 12 hours to obtain the bimetal coordination sulfide self-sustaining activated mercury removal adsorbent copper molybdenum sulfide;
(3) Respectively weighing 30mg of adsorbent in a 6mm quartz reaction tube, wherein the zero-valent mercury concentration in simulated flue gas input by an inlet is 1.8mg/m 3 The total flow is 500mL/min, the reaction temperature is 80 ℃, and the mercury adsorption efficiency reaches 87% in 3 hours;
(4) After further introducing 5000ppm sulfur dioxide and 5% water vapor, the mercury removal efficiency increased to 98% and maintained stable mercury removal efficiency for over 300min.
Example 3
The preparation of the zinc-molybdenum bimetal coordination type sulfide self-sustaining activated mercury removal adsorbent and mercury adsorption comprise the following steps:
(1) Respectively weighing 0.1mol of ammonium tetrathiomolybdate and 0.1mol of zinc chloride, adding 50mL of deionized water for dissolution, slowly dropwise adding the zinc chloride solution into the ammonium tetrathiomolybdate solution, stirring for 3 hours, and centrifuging to separate precipitate;
(2) Freezing at-80 ℃ for 6 hours, and freeze-drying at-50 ℃ for 12 hours to obtain the bimetal coordination sulfide self-sustaining activated mercury removal adsorbent zinc molybdenum sulfide;
(3) Respectively weighing 30mg of adsorbent in a 6mm quartz reaction tube, wherein the zero-valent mercury concentration in simulated flue gas input by an inlet is 1.8mg/m 3 The total flow is 500mL/min, the reaction temperature is 80 ℃, and the mercury adsorption efficiency reaches 45% in 3 hours;
(4) When 5000ppm sulfur dioxide and 5% water vapor were further introduced, the mercury removal efficiency increased to 58% and maintained stable mercury removal efficiency for over 300min.
Example 4
The preparation of the cadmium-molybdenum bimetallic coordination sulfide self-sustaining activated mercury removal adsorbent and mercury adsorption comprise the following steps:
(1) Respectively weighing 0.1mol of ammonium tetrathiomolybdate and 0.1mol of cadmium chloride, adding 50mL of deionized water for dissolution, slowly dropwise adding the cadmium chloride solution into the ammonium tetrathiomolybdate solution, stirring for 3 hours, and centrifuging to separate precipitate;
(2) Freezing at-80 ℃ for 6 hours, and freeze-drying at-50 ℃ for 12 hours to obtain the bimetal coordination sulfide self-sustaining activated mercury removal adsorbent cadmium molybdenum sulfide;
(3) Respectively weighing 30mg of adsorbent in a 6mm quartz reaction tube, wherein the zero-valent mercury concentration in simulated flue gas input by an inlet is 1.8mg/m 3 The total flow is 500mL/min, the reaction temperature is 80 ℃, and the mercury adsorption efficiency reaches 77% after 3 hours;
(4) After further introducing 5000ppm sulfur dioxide and 5% water vapor, the mercury removal efficiency increased to 83% and maintained stable mercury removal efficiency for over 300min.
Example 5
Al (aluminum) alloy 2 O 3 Preparation of a ZnS-based self-sustaining activated (hydrogen sulfide-assisted) mercury removal sorbent and mercury adsorption, comprising the steps of:
(1) 1mmol of zinc sulfate is weighed, dissolved in 5mL of deionized water, added with 5g of commercial gamma-alumina pellets with the diameter of 1.5mm, and dried in an oven at 80 ℃ for 6h after ultrasonic treatment for 45 min;
(2) Weighing 1mmol of sodium sulfide nonahydrate, dissolving in 20mL of deionized water, pouring into the materials, transferring to a 50mL Teflon-lined reaction kettle, performing hydrothermal reaction at 120 ℃ for 12h, cooling after the reaction, filtering, respectively washing with deionized water and ethanol for three times, and drying at 80 ℃ for 12h to obtain Al 2 O 3 A ZnS-based self-sustaining activated mercury removal sorbent;
(3) Weighing 0.5g of adsorbent in a 10mm quartz reaction tube, wherein the zero-valent mercury concentration in simulated flue gas input by an inlet is 1.8mg/m 3 The total flow is 360mL/min, the reaction temperature is 80 ℃, and the mercury adsorption efficiency is 10%;
(4) When 5000ppm sulfur dioxide, 5% water vapor and 100ppm hydrogen sulfide are introduced and activated for 15min, the hydrogen sulfide is turned off, the mercury removal efficiency is improved to 95%, and the mercury removal efficiency is still as high as 90% after 10h of reaction.
The effect of the self-sustaining activated adsorbent of the present invention will be further described below by taking waste gas containing mercury and sulfur oxides produced in nonferrous metal smelting industry in a certain factory as an example.
Example 6
Al (aluminum) alloy 2 O 3 Preparation, mercury adsorption and cyclic regeneration of a self-sustaining activated (hydrogen sulfide assisted) mercury removal adsorbent based on CuS, comprising the following steps:
(1) 1mmol of copper sulfate is weighed, dissolved in 5mL of deionized water, added with 5g of commercial gamma-alumina pellets with the diameter of 1mm, and dried in a 60 ℃ oven for 6h after ultrasonic treatment for 30min;
(2) Weighing 1mmol of sodium sulfide nonahydrate, dissolving in 50mL of deionized water, pouring into the materials, transferring to a reaction kettle with a 100mL Teflon lining, carrying out hydrothermal reaction at 120 ℃ for 12h, filtering after cooling down, respectively washing with deionized water and ethanol for three times, and drying at 60 ℃ for 12h to obtain Al 2 O 3 The @ CuS-based self-sustained activated mercury removal adsorbent;
(3) Weighing 0.5g of adsorbent in a 10mm quartz reaction tube, wherein the zero-valent mercury concentration in the imported waste gas is 2.5mg/m 3 Sulfur dioxide concentration is 0.5%, water vapor concentration is 5%, total flow is 500mL/min, reaction temperature is 40 ℃, initial mercury adsorption efficiency reaches 95%, and the reaction time is reduced to 45% after 300min;
(4) After 100ppm of hydrogen sulfide is introduced and activated for 30min, the hydrogen sulfide is closed, the mercury removal efficiency is improved to 95%, and the stable mercury removal efficiency is maintained to be more than 300min;
(5) After 24 hours, the mercury removal efficiency is reduced to 50%, 100ppm of hydrogen sulfide is introduced again to activate for 30 minutes, and then the hydrogen sulfide is closed, so that the mercury removal efficiency is improved to 90%;
(6) After six rounds of activation (30 min) -adsorption (24 h) reactions, the adsorbent can still repeatedly improve the activity, and the mercury adsorption capacity reaches 202.4mg/g (normalized to copper sulfide load).
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The regeneration method of the self-sustaining activated adsorbent for removing mercury from high-sulfur high-humidity flue gas is characterized by comprising the following steps of:
s21, using the self-sustaining activated adsorbent to treat high-sulfur high-humidity flue gas, and utilizing the characteristics of the high-sulfur high-humidity flue gas, performing a reverse disproportionation reaction between sulfur dioxide gas and low-valence sulfur species on the surface of the self-sustaining activated adsorbent to form a sulfur etching effect, wherein generated nascent sulfur forms a new active site under the induction of transition metal ions, so that site reconstruction and self-sustaining activation effects are realized;
s22, when the consumption of low-valence sulfur on the surface of the self-sustained activated adsorbent is lower than 50% or the adsorption efficiency of mercury is lower than 50%, intermittently adding hydrogen sulfide gas into the flue gas from the upstream of the adsorption device, wherein the hydrogen sulfide gas is adsorbed by the self-sustained activated adsorbent and is supplemented to the surface of the self-sustained activated adsorbent as low-valence sulfur when passing through the adsorbent layer, so that the self-sustained activated adsorption performance is recovered;
s23, when the mercury adsorption on the self-sustained activated adsorbent is enriched to be higher than 100g/kg, taking out, and then collecting and recycling the regenerated mercury by using a heating regeneration and condensation method, wherein the regenerated self-sustained activated adsorbent is recycled after being subjected to hydrogen sulfide gas reactivation;
the self-sustaining activated adsorbent for removing mercury in the high-sulfur and high-humidity flue gas is simple metal sulfide composed of single transition metal element and sulfur element, or coordination metal sulfide composed of two or more transition metal elements and sulfur element;
the self-sustaining activation effect in the step S21 means that under the wet flue gas, high-concentration sulfur dioxide can undergo a reverse disproportionation reaction with sulfur sites of a wet interface of an adsorption material to continuously generate active sites, so that high-capacity adsorption, enrichment and recovery of mercury are realized;
the high-sulfur high-humidity flue gas in the step S21 is mercury-containing and oxysulfide-containing waste gas produced by the nonferrous metal smelting industry, and the temperature is 20-80 ℃ and the relative humidity is 60-95% after wet washing; mercury in the high-sulfur high-humidity flue gas after wet washing mainly exists in a zero-valent mercury form; the concentration of sulfur dioxide gas is 0.5-10%.
2. The method for regenerating the self-sustaining activated adsorbent for removing mercury from high-sulfur and high-humidity flue gas according to claim 1, wherein the transition metal element is a ds zone element, and the ds zone element belongs to a sulfur-philic element and is easy to form metal sulfide with sulfur.
3. The method for regenerating a self-sustaining activated adsorbent for removing mercury from high sulfur and high humidity flue gas according to claim 2, wherein said transition metal element is one or more selected from the group consisting of copper, zinc, silver, cadmium and mercury.
4. The method for regenerating the self-sustaining activated adsorbent for removing mercury from high-sulfur and high-humidity flue gas according to claim 1, wherein the method for preparing the self-sustaining activated adsorbent comprises the following steps:
s11, selecting transition metal salt and a sulfur source as precursors, and synthesizing a metal sulfide adsorbent by a precipitation method or a hydrothermal method;
and S12, forming the metal sulfide adsorbent in a post-treatment mode, so as to realize high exposure and activation treatment of sulfur sites on the surface of the metal sulfide adsorbent, and obtain the self-sustaining activated adsorbent for removing mercury.
5. The method for regenerating a self-sustaining activated adsorbent for removing mercury from high-sulfur and high-humidity flue gas according to claim 4, wherein in the step S11, the transition metal salt is selected from one or more of chloride, sulfate, nitrate and acetate, the sulfur source is selected from one or more of elemental sulfur, sodium sulfide, thioacetamide and thiourea, and the molar ratio of the transition metal element in the transition metal salt to the sulfur element in the sulfur source is 1 (0.5-1.5);
the reaction temperature of the precipitation method is room temperature, and the reaction time is 0.5-6h;
the reaction temperature of the hydrothermal method is 120-180 ℃ and the reaction time is 6-12h.
6. The method for regenerating the self-sustaining activated adsorbent for removing mercury from high-sulfur and high-humidity flue gas according to claim 4, wherein the specific steps of the post-treatment mode in step S12 are as follows: high exposure of sulfur sites is achieved by supercritical drying, freeze drying or vacuum drying; the activation of sulfur sites is achieved by solid-liquid phase ion exchange, utilizing the solubility differences between different sulfides.
7. The method for regenerating a mercury-removing self-sustaining activated adsorbent for high-sulfur and high-humidity flue gas according to claim 1, wherein the mercury concentration in the high-sulfur and high-humidity flue gas after wet washing in step S21 is 0.05-50mg/m 3 ；
The low-valence sulfur includes sulfur ions that are eluted from the self-sustaining activated sorbent interface itself.
8. The method for regenerating the self-sustaining activated adsorbent for removing mercury from high-sulfur and high-humidity flue gas according to claim 1, wherein the self-sustaining activated adsorbent in step S21 adopts a fixed bed or moving bed mode to treat the high-sulfur and high-humidity flue gas, and the space velocity used in the treatment is 1000-20000h -1 。
9. The method for regenerating a mercury removal self-sustaining activated adsorbent for high sulfur and high humidity flue gas according to claim 1, wherein the concentration of hydrogen sulfide gas in step S22 is 10-200ppm.
10. The method for regenerating the self-sustaining activated adsorbent for removing mercury from high-sulfur and high-humidity flue gas according to claim 1, wherein the specific steps of the heating regeneration and condensation method in the step S23 are as follows: heating the self-sustaining activated adsorbent to 250-350 ℃ to obtain high-concentration zero-valent mercury gas, condensing and adsorbing to recover zero-valent mercury products; the regenerated self-sustaining activated adsorbent is cooled and then activated for 5-30min by hydrogen sulfide gas with the concentration of 10-200ppm.
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