CN117563556A - Renewable load-type desulfurizing agent and preparation method thereof - Google Patents
Renewable load-type desulfurizing agent and preparation method thereof Download PDFInfo
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- CN117563556A CN117563556A CN202410060773.2A CN202410060773A CN117563556A CN 117563556 A CN117563556 A CN 117563556A CN 202410060773 A CN202410060773 A CN 202410060773A CN 117563556 A CN117563556 A CN 117563556A
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- Prior art keywords
- desulfurizing agent
- agent
- sulfur
- surfactant
- pore
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000011069 regeneration method Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 45
- 230000008929 regeneration Effects 0.000 claims abstract description 45
- 238000001179 sorption measurement Methods 0.000 claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 34
- 230000023556 desulfurization Effects 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000003623 enhancer Substances 0.000 claims abstract description 14
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920002472 Starch Polymers 0.000 claims abstract description 4
- 235000019698 starch Nutrition 0.000 claims abstract description 4
- 239000008107 starch Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- -1 sorbitol fatty acid ester Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 59
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 17
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 17
- 239000002912 waste gas Substances 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- HJIYJLZFNBHCAN-UHFFFAOYSA-N [V].[C] Chemical compound [V].[C] HJIYJLZFNBHCAN-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 2
- 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 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZMMDPCMYTCRWFF-UHFFFAOYSA-J dicopper;carbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[O-]C([O-])=O ZMMDPCMYTCRWFF-UHFFFAOYSA-J 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/26—Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a renewable load-type desulfurizing agent and a preparation method thereof, wherein the renewable load-type desulfurizing agent comprises the following raw materials in parts by mass: 100 parts of active carbon and 150-250 parts of impregnating solution, wherein the impregnating solution comprises metal nitrate, surfactant, pore-forming agent starch and strength enhancer nano SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The renewable supported desulfurization agent is activated carbon leachingSoaking in the soaking solution, taking out, drying, and calcining under inert atmosphere. The desulfurizing agent has high adsorption efficiency on sulfide in waste gas, has good regeneration performance, regenerates the desulfurizing agent by adopting a small amount of purified industrial gas at high temperature in situ, realizes the recycling of the desulfurizing agent and the sulfur-containing industrial gas, and has strong hydrogen sulfide adsorption capability. The method of the invention is simple, low in investment and low in operation cost.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a renewable load type desulfurizing agent and a preparation method thereof.
Background
The steel production mainly takes a long process, and a large amount of blast furnace gas is generated in the blast furnace ironmaking process. The yield of blast furnace gas is about 1500-2000Nm per ton of iron 3 The main component is CO 2 (16~22％)、CO(18~24％)、H 2 (0.5~2.5％)、 N 2 (56-63％)、C x H y (2-4%), and also dust, moisture, small amounts of chlorides and small amounts of sulfur-containing species, wherein the sulfur-containing species are in the form of COS, H 2 S is mainly the concentration of 80-220 mg/m 3 Heat value 3000-4000kJ/Nm 3 The tapping temperature is 100-160 ℃. The blast furnace gas is usually sent to a hot blast stove, a heating furnace, a boiler, a gas unit and the like in a fuel mode for combustion, and sulfide in the blast furnace gas can be burnt to form SO 2 Is discharged into the air.
Currently, four blast furnace gas desulfurization methods are industrially applied in China, and the first method is hydrolysis and active carbon dry desulfurization technology; the second is hydrolysis + wet desulfurization technology; the third is NSAD (Nature Sulfur Autotrophic Denitrifi-cation) desulfurization technology; the fourth is the microcrystalline adsorption desulfurization technique. The active carbon dry desulfurization technology has the defects of large filling amount of desulfurizing agent, frequent replacement of the desulfurizing agent, treatment of the desulfurizing agent and the like. Both NSAD and microcrystalline adsorption desulfurization technologies are renewable dry desulfurization technologies, and have the defects of short service life, high running cost and the like due to higher regeneration temperature and difficult regeneration. The existing desulfurizing agent can not meet the actual industrial application requirements, and the development of a novel renewable solid desulfurizing agent with high desulfurizing efficiency, speed and selectivity is still one of the targets of gas desulfurization technology.
University of Zhejiang CN100560185C discloses a renewable load type desulfurizing agent and a preparation method thereof. The ionic polymer is loaded on the porous solid material, and the desulfurizing agent has the advantages of high absorption rate, good selectivity and large absorption capacity; the regeneration is easy, and the water purifier can be recycled for multiple times; the mechanical strength is high, and the mechanical strength and the absorption performance of the water vapor are not affected after the water vapor is absorbed to a certain extent; the desorption tolerance temperature is high. However, the preparation cost is high, the preparation process is complex, and the polymerization process needs 6-12 hours. The China academy of sciences Shanxi coal chemistry institute CN1102424C discloses a method for regenerating a copper series desulfurizing agent, which comprises the steps of heating the sulfur-absorbed and saturated copper series desulfurizing agent to 300-500 ℃ in an ammonia-containing gas atmosphere with a space velocity of 700-1200h -1 The regeneration time is 30-60 minutes. The invention has the advantages of simple regeneration process, easy operation, no reduction of activity of the desulfurizer after regeneration, no strong exothermic reaction during secondary desulfurization, no pre-oxidation treatment after regeneration, direct use for desulfurization, convenient storage and transportation of liquid ammonia, and low comprehensive desulfurization cost. However, this method has a high regeneration temperature and a high device cost. CN100376310C provides a method for regenerating vanadium-carbon-based desulfurizing agent: the sulfur-absorbing V/AC composite desulfurizing agent containing transition metal is filled into a regeneration reactor and H is used 2 The gas is used as a reducing agent, a transition metal catalyst is added into a vanadium-carbon-based composite desulfurizing agent containing transition metal or a vanadium-carbon desulfurizing agent without transition metal, and a closed circulation gas circuit is adopted for regeneration. Solid sulfur is obtained in the process, so that the subsequent treatment is avoided. The regenerated recycle gas can be reused. CN101664689B relates to a method for preparing active carbon desulfurizing agent by using a hybrid fresnel method and a method thereof. Mixing cupric oxide or basic cupric carbonate and pulverized coal or charcoal powder with a certain amount of water, adding tar, rolling, extruding to form strips, drying, and activating to obtain the final product. The active carbon desulfurizer prepared by the method has more developed pore system and specific surface area exceeding 1000m than the active carbon desulfurizer prepared by the impregnation method 2 And/g, the desulfurizing agent is activated by water vapor, the activation temperature is 850 ℃, and the activation time is 180 minutes.
CN102500323B provides a modified active carbon desulfurizing agent and its preparation method and useA method for treating hydrogen sulfide waste gas. The modified active carbon desulfurizing agent is obtained by impregnating active carbon with an active agent mixed solution comprising phenol, acetone, sodium carbonate, ferric nitrate and an organic solvent, and then drying and roasting. The modified active carbon desulfurizing agent of the invention converts hydrogen sulfide in waste gas into sulfur dioxide under normal temperature and pressure by utilizing the adsorption and catalytic oxidation action, and then is converted into SO in water phase by washing 4 2- And is removed. Avoiding the defect that the desulfurizing agent needs to be periodically desorbed and regenerated due to the blockage caused by saturated adsorption and the generation of elemental sulfur. Compared with the common active carbon desulfurization process, the process has the advantages of high hydrogen sulfide removal rate, long service life of the desulfurizing agent, low operation cost, simple operation and management and the like. Chinese patent CN1415402A uses ZnO-TiO as main component 2 -Al 2 O 3 Can be used as desulfurizing agent of H 2 S and organic sulfur are removed simultaneously, but the sulfur removal agent is required to be used at a high temperature of 180-320 ℃ and has high requirements on application conditions. CN1186841a proposes a modified activated carbon for desulfurizing waste gas at normal temperature, which can be used for purifying chemical raw material gases such as synthetic ammonia, petroleum and natural gas, but mainly aims at organic sulfides (such as CS 2 ) Has good absorption effect on inorganic sulfides (such as sulfur H) 2 S) the treatment effect of the gas is poor, and the modified activated carbon is used as a desulfurizing agent to remove hydrogen sulfide in the waste gas, so that the hydrogen sulfide is required to be periodically desorbed, regenerated, cleaned or replaced, and the defects of continuous reduction of the hydrogen sulfide removal rate along with the prolonging of the service time of the desulfurizing agent, short service life of the desulfurizing agent, high operation cost, complex operation management and the like exist.
The desulfurizing agent has the defects of high desulfurizing agent preparation cost, long preparation flow, low sulfur capacity, complex desulfurizing agent regeneration process, high regeneration temperature, poor inorganic sulfide hydrogen sulfide treatment effect, short service life and the like. The invention aims to provide a renewable and industrially applicable blast furnace gas desulfurizing agent and an application method thereof. The desulfurizing agent is subjected to chemical adsorption on hydrogen sulfide generated after hydrolysis of blast furnace gas at a lower temperature, and is regenerated at a high temperature by using part of purified blast furnace gas after adsorption saturation, and contains a large amount of carbonyl sulfide and hydrogen sulfideIs combusted in the sintering section to convert hydrogen sulfide and carbonyl sulfide into SO 2 And then desulfurization treatment is carried out.
Disclosure of Invention
The invention aims to provide a renewable supported metal oxide desulfurizer, and the active substances on the supported metal oxide desulfurizer can be one or two of copper oxide, zinc oxide, ferric oxide and manganese oxide, and the addition of the active substances improves the thermal stability of the desulfurizer, and the adsorbent has higher desulfurization performance due to the synergistic effect of the metal oxides. The invention adopts the compound surfactant, the pore-forming agent and the strength enhancer, and enhances the mechanical strength of the carrier while keeping the specific surface area and the pore structure of the carrier increased. The desulfurizing agent obtained by the invention adopts the principle of temperature swing adsorption, is adsorbed at low temperature, and is regenerated by partially purified blast furnace gas at high temperature in situ, so that the recycling of the desulfurizing agent is realized, the hydrogen sulfide adsorption capability is strong, the regeneration system is simple, and the physical loss of the adsorbent is avoided. The running cost is far lower than that of disposable adsorbents.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the renewable supported desulfurizing agent comprises the following raw materials in parts by mass: 100 parts of active carbon and 150-250 parts of impregnating solution, wherein the impregnating solution comprises metal nitrate, surfactant, pore-forming agent starch and strength enhancer nano SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The renewable load type desulfurizing agent is obtained by dipping active carbon in dipping liquid, taking out, drying and calcining under inert atmosphere; the metal nitrate is selected from Fe (NO) 3 ) 3 、Cu(NO 3 ) 2 、Mn(NO 3 ) 2 、Zn(NO 3 ) 2 At least one of them.
Further, the ratio of the activated carbon to the impregnating solution satisfies the isovolumetric impregnation method, that is, the activated carbon is impregnated in the impregnating solution of saturated adsorption amount of the activated carbon.
Further, the specific surface area of the activated carbon is 250-350 m 2 Per gram, pore volume of 0.25-0.3. 0.3 cm 3 /g, pore diameter 5.5-6nm; the watchThe surfactant is selected from nonionic surfactant and/or anionic surfactant, the nonionic surfactant is selected from at least one of fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyoxyethylene ether sorbitol fatty acid ester and laurinol polyoxyethylene ether, the anionic surfactant is selected from at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, and the strength enhancer is nano SiO 2 The particle size of (2) is 200-400nm.
Further, in the impregnating solution, the solvent is at least one selected from methanol, ethanol and isopropanol, the molar concentration of metal nitrate is 1-2M, the mass concentration of the surfactant is 20-30 g/L, the mass concentration of the pore-forming agent is 40-50g/L, and the mass concentration of the strength enhancer is 20-30 g/L.
Preferably, the impregnating solution also comprises 0.01-0.02M La (NO) 3 ) 3 And 0.05-0.08M Co (NO) 3 ) 2 . The inventor has unexpectedly found that the desulfurization effect of the obtained load type desulfurizing agent is not changed by adding a small amount of lanthanum and cobalt into the impregnating solution, but the regeneration capability of the load type desulfurizing agent is obviously improved, the load type desulfurizing agent circulates for 100 times after regeneration, the sulfur capacity and the sulfur capacity after the first regeneration are little attenuated, and the load type desulfurizing agent has excellent desulfurizing agent regeneration capability; more importantly, the regeneration of the desulfurizing agent can achieve good regenerating effect of the desulfurizing agent by using a small amount of regeneration process gas at a lower temperature. The inventors have also found that the best regeneration capacity improvement can be achieved only by compounding lanthanum and cobalt, so that other rare earth metals such as Ce and Y are added in the same molar amount; or other transition metals with the same molar quantity are added to replace Co, and the effect of improving the regeneration capability of the desulfurizing agent by adding La and Co cannot be achieved. The invention also provides a preparation method of the renewable load type desulfurizing agent, which comprises the following steps:
(S1) dispersing metal nitrate, a surfactant, a pore-forming agent and a strength enhancer in an alcohol solvent, and fully mixing to obtain an impregnating solution;
and (S2) under the ultrasonic and stirring conditions, soaking the activated carbon in the soaking solution, filtering, drying to obtain a carrier loaded with the active metal compound, and roasting in an inert atmosphere to obtain the modified activated carbon desulfurizing agent.
Further, in the step (S1), the activated carbon is subjected to alkali treatment, specifically: adding active carbon into a solution containing sodium hydroxide/potassium carbonate/potassium hydroxide at 60-80 ℃ for alkali washing, and then drying at 60-80 ℃.
Further, in the step (S2), the impregnation is carried out at 20-40 ℃ for 10-15 hours; drying is not particularly limited, such as oven drying, vacuum drying; roasting for 2-4 hours at 240-300 ℃ in an inert atmosphere; the inert atmosphere is nitrogen and/or argon; the roasting is carried out for 3-5 hours at 240-300 ℃.
Further, in the step (S2), 0.01-0.02M La (NO) is added in the preparation of the impregnating solution 3 ) 3 And 0.05-0.08M Co (NO) 3 ) 2 . In the impregnating solution, the molar concentration of metal nitrate is 1-2M, the mass concentration of surfactant is 20-30 g/L, the mass concentration of pore-forming agent is 40-50g/L, and the concentration of strength enhancer is 20-30 g/L.
Further, in step (S2), the conditions of sonication and stirring are well known in the art, such as stirring speeds of 500-800rpm and ultrasonic frequencies of 100-160kHz.
The invention also provides a method for desulfurizing industrial gas, which comprises the following steps: and (3) carrying out adsorption desulfurization on the sulfur-containing industrial gas by the renewable load-type desulfurizing agent.
Further, the sulfur-containing industrial gas is an industrial waste gas containing hydrogen sulfide and carbon monoxide, such as blast furnace gas, coke oven gas, and converter gas. The desulfurizing agent of the invention carries out desulfurization treatment on industrial waste gas containing hydrogen sulfide and carbon monoxide, and the desulfurizing agent which is saturated by adsorption can be regenerated by adopting the gas after desulfurization and purification, namely, the regenerated gas is from the gas after purification treatment, and the introduction of the regenerated process gas is not needed. The sulfur-containing industrial gas contains 100-300 mg/m 3 H 2 S,15-30 vol% CO; such as blast furnace gas, which contains 100-300 mg/m 3 H 2 S，15-30 vol%CO 2 15-30 vol% CO,1-3 vol% H 2 The balance being N 2 And inevitablyImpurities; h in purified industrial gas 2 S and COS (carbonyl sulfide) contents lower than 10 mg/m 3 。
Further, the adsorption temperature is 50-80 ℃, such as 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃; the adsorption airspeed is 500-3000h -1 Such as 1500h -1 、2000h -1 、2500h -1 。
The invention also provides a regeneration method of the desulfurizing agent, which adopts the principle of temperature swing adsorption and comprises the following steps: regenerating the desulfurizing agent with saturated adsorption at 120-180 ℃ by using industrial gas after desulfurization and purification, wherein the purified industrial gas H 2 S and COS contents lower than 10 mg/m 3 The volume of the purified sulfur-containing industrial gas used in the regeneration is 3-5% of the volume of the sulfur-containing industrial gas saturated by the desulfurizing agent. For example, the sulfur-containing industrial gas is blast furnace gas. The determination method of adsorption saturation is well known in the art, such as detecting H in tail gas 2 S and COS contents, to H 2 The total content of S and COS exceeds 10 mg/m 3 After that, adsorption saturation was considered to be reached.
The desulfurizer prepared by the invention has excellent regeneration capability, can complete regeneration by adopting less purified blast furnace gas (3-5% of the volume of the blast furnace gas which enables the desulfurizer to reach adsorption saturation) at a lower temperature (120-180 ℃), can complete regeneration by using a small amount of desulfurized industrial gas without additional preparation, avoids energy loss of high-temperature regeneration, and simultaneously reduces physical loss of the desulfurizer and the defect of needing a large amount of regenerated process gas. The sulfur adsorption capacity of the regenerated desulfurizing agent is about two thirds of that of the fresh desulfurizing agent before regeneration, but basically the same sulfur adsorption capacity can be maintained after 100 regeneration cycles. The desulfurizing agent has the advantages of simple regeneration process, low cost, basically no reduction of the regenerated 100 times of sulfur capacity, and extremely strong low-cost desulfurizing process in industry. The desulfurizing agent is suitable for desulfurizing sulfur-containing gas containing carbonyl sulfide and hydrogen sulfide, and converts the hydrogen sulfide and the carbonyl sulfide into SO 2 Then desulfurization treatment is carried out, and the regenerated gas is purified blast furnace gas after desulfurization, thereby realizing desulfurizing agent and gasAnd (5) recycling.
The invention has the following beneficial effects:
1. the carrier is prepared by taking the coal activated carbon with wide sources as the raw material, and the loaded alkaline substance can react with hydrogen sulfide, so that the chemical adsorption effect of the activated carbon is obviously improved; the active carbon is loaded with activated metal to adsorb sulfur atoms in sulfide, so that the sulfur atoms are reserved on the adsorbent, and the active carbon has high adsorption efficiency on sulfide in waste gas; the compound surfactant, the pore-forming agent and the strength enhancer are adopted, so that the mechanical strength of the carrier is enhanced while the specific surface area and the pore structure of the carrier are increased.
2. The desulfurizing agent obtained by the invention has good regeneration performance, adopts the principle of temperature swing adsorption, is adsorbed at low temperature, adopts a small amount of purified sulfur-containing industrial gas, such as blast furnace gas after desulfurization purification, to regenerate the desulfurizing agent at high temperature in situ, realizes the recycling of the desulfurizing agent and the sulfur-containing industrial gas, and has strong hydrogen sulfide adsorption capability. The method of the invention is simple, low in investment and low in operation cost.
Drawings
FIG. 1 is a graph showing the distribution of the pore diameters of the desulfurizing agent obtained in example 1;
FIG. 2 is a graph showing the sulfur capacity of the desulfurizing agent obtained in example 1 after the circulating regeneration.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. The following examples facilitate a better understanding of the present invention, but are not intended to limit the same. The experimental methods in the following examples are conventional methods unless otherwise specified.
The BET of the activated carbon used in the examples of the present invention was 317m 2 Per gram, average pore volume 0.27cm 3 And/g, average pore size 5.75nm.
Example 1
Preparing a desulfurizing agent:
(S1) taking active carbon as a carrier, taking sodium hydroxide as an impregnating solution, and adding 0.1mol/L sodium hydroxide solution into the carrier according to an isovolumetric impregnation method; soaking for 20h at 20 ℃, filtering, and drying the solid at 80 ℃ for 6h to obtain alkali-treated activated carbon;
(S2) 43.53g of Fe (NO) 3 ) 3 2.5g of compound surfactant (compound of fatty alcohol polyoxyethylene ether and sodium dodecyl benzene sulfonate according to the mass ratio of 1:1), 4g of pore-forming agent starch and 2.5g of strength enhancer SiO 2 Dispersing in 100mL of solvent methanol, and fully mixing to obtain an impregnating solution, wherein the concentration of metal Fe ions is 1.8 mol/L;
(S3) according to the isovolumetric impregnation method, 10g of the alkali-treated activated carbon obtained in the step (S1) is impregnated in 19.5g of the impregnation liquid obtained in the step (S2) under the conditions of 120 kHz ultrasonic and 600 rpm stirring at room temperature for 12 hours, the solid is dried for 6 hours at 80 ℃ after filtration, and then baked for 3 hours at 300 ℃ under the nitrogen atmosphere, so as to obtain the desulfurizing agent 1, ICP test, fe 2 O 3 The content was 9.3%.
FIG. 1 is a graph showing the distribution of the most probable pore diameter of the desulfurizing agent prepared in example 1, wherein the most probable pore diameter is about 3.9nm, and the adsorbent has smaller pore diameter and is beneficial to the dispersion of active components.
Adsorption and regeneration:
adsorption process: blast furnace gas composition: 200 mg/m 3 H 2 S，20 vol%CO 2 20 vol% CO, the rest of N 2 The mixture enters an adsorption tube from top to bottom for adsorption under normal pressure, the adsorption temperature is controlled at 60 ℃, and the adsorption airspeed is about 2000 h -1 Monitoring H in tail gas using Fu Li gas chromatograph 2 S and COS contents, to H 2 The total content of S and COS exceeds 10 mg/m 3 Adsorption saturation is described later, and adsorption is stopped.
The regeneration process comprises the following steps: introducing the gas subjected to the adsorption desulfurization purification from bottom to top for regeneration, wherein the gas consumption after the adsorption desulfurization purification is 3% of the adsorption saturation volume of the desulfurizing agent, and the regeneration airspeed is about 200h -1 And (3) the regeneration temperature is 150 ℃, the tail gas is connected with the GC, the content change of sulfide is monitored, the temperature is reduced to 60 ℃ after the regeneration is finished, and the steps are repeated for a plurality of adsorption-regeneration cycles, so that the change of sulfur capacity and the regeneration condition are obtained. FIG. 2 is a graph showing the sulfur capacity change of 100 experiments on the desulfurizing agent obtained in example 1.
Example 2
The other conditions were the same as in example 1, except that in step (S2), the metal nitrate Fe (NO 3 ) 3 Replaced by equimolar amount of Cu (NO) 3 ) 2 。
Example 3
The other conditions were the same as in example 1, except that in step (S2), the metal nitrate Fe (NO 3 ) 3 Replaced by equimolar amount of Zn (NO 3 ) 2 。
Example 4
The other conditions were the same as in example 1, except that in step (S2), the metal nitrate Fe (NO 3 ) 3 Replaced by equimolar amount of Cu (NO) 3 ) 2 、Fe(NO 3 ) 3 Mixed solution, wherein Cu: molar ratio of fe=1:1.
Example 5
The other conditions were the same as in example 1 except that in step (S2), 0.02M La (NO 3 ) 3 And 0.05M Co (NO 3 ) 2 。
Example 6
The other conditions were the same as in example 1 except that in step (S2), 0.01M La (NO 3 ) 3 And 0.08M Co (NO) 3 ) 2 。
Example 7
The other conditions were the same as in example 1 except that in step (S2), 0.07M La (NO 3 ) 3 。
Example 8
The other conditions were the same as in example 1 except that in step (S2), 0.07M Co (NO 3 ) 2 。
Example 9
The other conditions were the same as in example 1 except that in step (S2), 0.02M of Y (NO) was added to the preparation of the impregnation liquid 3 ) 3 And 0.05M Co (NO 3 ) 2 。
The following performance tests were conducted on the desulfurizing agents obtained in the above examples, and the results are shown in Table 1 below.
1. Mechanical strength: and referring to the abrasion resistance and compressive strength of the 3 rd part of the test method of the coal particle activated carbon for GBT 30202.3-2013 desulfurization and denitrification.
An intelligent ZQJ-II particle strength tester (manufactured by Dalian intelligent tester), national chemical catalyst detection center (national chemical catalyst detection center) was used. Randomly taking 20 composite adsorbent microspheres to test the compressive strength, and taking an average value.
Abrasion resistance = value of sample mass remaining on the sieve layer after test/value of sample mass before test x 100%
2. Sulfur capacity:
；
wherein:sulfur capacity, unit is mg/g;
Vthe unit is mL/min for the air inlet flow;
tthe unit is min for adsorption penetration time;
Cis H in the raw material gas 2 S concentration in mg/m 3 ；
mThe mass of the desulfurizing agent is expressed in g.
TABLE 1 desulfurizing agent Performance test results
。
FIG. 2 is a graph showing the sulfur capacity of the desulfurizing agent obtained in example 1 after the circulating regeneration. It can be seen that the sulfur capacity of the regenerated desulfurizing agent can reach more than 60% of that of the fresh desulfurizing agent, and after 100 regeneration cycles, the sulfur capacity can also be basically maintained as that of the first regeneration.
As can be seen from Table 1, the intensity and abrasion rate of the desulfurizing agent prepared by the method are obviously higher than those of the desulfurizing agent prepared by the conventional method, thus greatly prolonging the service life of the desulfurizing agent and reducing the use cost of the desulfurizing agent. The inventors have also unexpectedly found that,adding small amount of La (NO) into the soaking solution 3 ) 3 And Co (NO) 3 ) 2 The regeneration capacity of the desulfurizing agent can be obviously improved, and the sulfur capacity of the regenerated desulfurizing agent is improved. Whereas equimolar La (NO) 3 ) 3 Or Co (NO) 3 ) 2 Either La is replaced by other rare earth metals or Co is replaced by other transition metals, the purpose of improving the regeneration capacity of the desulfurizing agent cannot be effectively achieved. The method shows that a certain synergistic compounding effect exists between La and Co.
Claims (10)
1. The regenerable supported desulfurizing agent is characterized by comprising the following raw materials in parts by mass: 100 parts of active carbon and 150-250 parts of impregnating solution, wherein the impregnating solution comprises metal nitrate, surfactant, pore-forming agent starch and strength enhancer nano SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The renewable load type desulfurizing agent is obtained by dipping active carbon in dipping liquid, taking out, drying and calcining under inert atmosphere; the metal nitrate is selected from Fe (NO) 3 ) 3 、Cu(NO 3 ) 2 、Mn(NO 3 ) 2 、Zn(NO 3 ) 2 At least one of them.
2. The regenerable supported desulfurization agent of claim 1, wherein said activated carbon has a specific surface area of 250-350 m 2 Per gram, pore volume of 0.25-0.3. 0.3 cm 3 /g, pore diameter 5.5-6nm; the surfactant is selected from nonionic surfactant and/or anionic surfactant, the nonionic surfactant is selected from at least one of fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyoxyethylene ether sorbitol fatty acid ester and laurinol polyoxyethylene ether, the anionic surfactant is selected from at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, and the strength enhancer is nano SiO 2 The particle size of (2) is 200-400nm.
3. The regenerable supported desulfurization agent of claim 1, wherein the impregnating solution comprises at least one solvent selected from the group consisting of methanol, ethanol and isopropanol, wherein the molar concentration of metal nitrate is 1-2M, the mass concentration of surfactant is 20-30 g/L, the mass concentration of pore-forming agent is 40-50g/L, and the mass concentration of strength enhancer is 20-30 g/L, based on total metal.
4. The regenerable supported desulfurization agent of claim 1, wherein said impregnating solution further comprises 0.01-0.02M La (NO 3 ) 3 And 0.05-0.08M Co (NO) 3 ) 2 。
5. The method for producing a regenerable supported desulfurization agent as claimed in any one of claims 1 to 4, comprising the steps of:
(S1) dispersing metal nitrate, a surfactant, a pore-forming agent and a strength enhancer in an alcohol solvent, and fully mixing to obtain an impregnating solution;
and (S2) under the ultrasonic and stirring conditions, soaking the activated carbon in the soaking solution, filtering, drying to obtain a carrier loaded with the active metal compound, and roasting in an inert atmosphere to obtain the modified activated carbon desulfurizing agent.
6. The method according to claim 5, wherein in step (S1), the activated carbon is subjected to alkali treatment, specifically: adding active carbon into a solution containing sodium hydroxide/potassium carbonate/potassium hydroxide at 60-80 ℃ for alkali washing, and then drying at 60-80 ℃.
7. The method according to claim 5, wherein in the step (S2), the impregnation is carried out at 20 to 40℃for 10 to 15 hours; the roasting is carried out for 3-5 hours at 240-300 ℃.
8. The process according to claim 5, wherein in the step (S2), 0.01 to 0.02M of La (NO) is added to the impregnation solution 3 ) 3 And 0.05-0.08M Co (NO) 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the In the impregnating solution, the molar concentration of the metal nitrate is 1-2M and the mass concentration of the surfactant is 20 percent based on the total metal30 The mass concentration of the pore-forming agent is 40-50g/L, and the concentration of the strength enhancer is 30-40 g/L.
9. A method for desulfurizing industrial gas, comprising the steps of: adsorption desulfurization of sulfur-containing industrial gas by the regenerable supported desulfurization agent of any one of claims 1-4.
10. The method of claim 9, further comprising the step of regenerating the desulfurizing agent: regenerating the desulfurizing agent with saturated adsorption at 120-180 ℃ by using sulfur-containing industrial gas after desulfurization and purification;
the sulfur-containing industrial gas contains 100-300 mg/m 3 H 2 S,15-30 vol% CO, H in the purified industrial gas 2 S and carbonyl sulfur content below 10 mg/m 3 ；
The volume of the purified industrial gas used in the regeneration is 3-5% of the volume of the sulfur-containing industrial gas saturated by the desulfurizing agent.
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