CN113893872B - Method for regenerating catalyst containing manganese oxide molecular sieve - Google Patents
Method for regenerating catalyst containing manganese oxide molecular sieve Download PDFInfo
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- CN113893872B CN113893872B CN202010572488.0A CN202010572488A CN113893872B CN 113893872 B CN113893872 B CN 113893872B CN 202010572488 A CN202010572488 A CN 202010572488A CN 113893872 B CN113893872 B CN 113893872B
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- CN
- China
- Prior art keywords
- molecular sieve
- regeneration
- oxide
- catalyst
- manganese oxide
- Prior art date
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Links
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 157
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 79
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 8
- 238000011069 regeneration method Methods 0.000 claims abstract description 67
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 53
- 230000008929 regeneration Effects 0.000 claims abstract description 51
- 238000000605 extraction Methods 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 9
- 230000023556 desulfurization Effects 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- WCMHZFHLWGFVCQ-UHFFFAOYSA-N [Ba].[Mn] Chemical compound [Ba].[Mn] WCMHZFHLWGFVCQ-UHFFFAOYSA-N 0.000 claims description 3
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 claims description 3
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 claims description 2
- UMRUNOIJZLCTGG-UHFFFAOYSA-N calcium;manganese Chemical compound [Ca+2].[Mn].[Mn].[Mn].[Mn] UMRUNOIJZLCTGG-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- 230000003009 desulfurizing effect Effects 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000000243 solution Substances 0.000 description 22
- 150000002697 manganese compounds Chemical class 0.000 description 18
- 238000005406 washing Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001027 hydrothermal synthesis Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000012265 solid product Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000012286 potassium permanganate Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 mn 2+ Chemical compound 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 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
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011701 zinc 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
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/56—Hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for regenerating a catalyst containing a manganese oxide molecular sieve, which comprises the following steps: placing a catalyst containing a manganese oxide molecular sieve after adsorbing hydrogen sulfide in an extraction cavity; introducing an organic solvent into the extraction chamber, performing extraction treatment, filtering and drying the obtained product, and then placing the product into a regeneration chamber; and introducing oxidizing gas into the regeneration chamber, heating the regeneration chamber to a regeneration temperature, and then maintaining the constant temperature for oxidation regeneration to recover the desulfurization activity of the manganese oxide molecular sieve-containing catalyst. The regeneration method of the invention is simple and easy to implement, has good repeatability, and the regenerated catalyst has stable property, can recover sulfur capacity, reduces the generation of dangerous waste and dangerous solid caused by frequent replacement of the catalyst, can reduce the cost of the desulfurizing agent and the environmental protection cost, and is beneficial to industrialized popularization.
Description
Technical Field
The invention relates to the field of catalyst regeneration, in particular to a method for regenerating a catalyst containing a manganese oxide molecular sieve.
Background
Hydrogen sulfide (H 2 S) is a corrosive toxic gas with malodorous odors that are present in air, water, natural gas, crude oil, industrial processes, and municipal and agricultural sewage. Hydrogen sulfide is a serious hazard to human health and also causes environmental pollution, and hydrogen sulfide is generated in many industrial production processes, for example, when water gas or semi-water gas is produced by using coke or anthracite as raw materials, hydrogen sulfide is generated in the production process of producing gas and natural gas by using heavy oil as raw materials through partial oxidation, and a great amount of hydrogen sulfide is also contained in catalytic hydrodesulfurization tail gas and flue gas discharged by coal-fired power plants. Other nitrogen fertilizer plants, agricultural chemical plants, leather manufacturing plants and other production processes can also generate a large amount of hydrogen sulfide gas. H 2 S existing in the industrial production process is considered as a harmful impurity, because it can not only harm human health and pollute the environment, but also cause problems of corrosion of chemical production equipment and pipelines, poisoning and deactivation of downstream catalysts, deterioration of product quality and the like. Many industrial processes have stringent requirements for the hydrogen sulfide content in the feed gas, for example, IGCC gas should have less than 20ppm hydrogen sulfide content, synthesis ammonia should have less than 1ppm hydrogen sulfide content, methanol synthesis gas and F-T synthesis oil feed gas should have less than 0.1ppm hydrogen sulfide content, and food grade carbon dioxide must have less than 0.1ppm hydrogen sulfide content. Therefore, the removal of hydrogen sulfide generated in the industrial production process has important significance, which can improve the atmospheric environment and the living quality of people; and the corrosion of hydrogen sulfide to equipment and pipelines and the poisoning of the catalyst can be avoided, so that the production efficiency and the product quality are improved.
The method for removing the hydrogen sulfide has a plurality of kinds, wherein the metal oxidant has high desulfurization efficiency and little pollution because of easily available raw materials. Common metal oxide dehydro-sulfide agents include zinc oxide, iron oxide, copper oxide, calcium oxide, manganese oxide and the like, and desulfurizing agents with different properties can be obtained due to different preparation methods and sources, so that the desulfurizing agents are used for different desulfurizing targets and application environments. The conventional oxide desulfurizer has the defects of low sulfur capacity, high bed penetration speed when high concentration of hydrogen sulfide, high desulfurization reaction temperature and the like, for example, the zinc oxide desulfurizer is easy to be reduced into Zn and evaporated at high temperature, so that active phase loss is caused; the manganese oxide desulfurizing agent is usually used for removing at medium and high temperature, and the sulfur capacity is lower at low temperature. The copper oxide desulfurizing agent is easy to be reduced into simple substance copper in high-temperature hydrogen-containing reducing atmosphere, so that the sulfur capacity is greatly reduced.
The desulfurizing agent is discharged after being adsorbed and saturated to form metal sulfide, belongs to solid waste and dangerous waste, and is treated according to the requirement of the national pollution environmental control method of solid waste of the people's republic of China and the corresponding regulation of the dangerous waste transfer joint management method. The desulfurizing agent with good regeneration performance not only has longer service cycle and service life, but also can save desulfurizing cost and reduce environmental pollution. The desulfurizing agent needs to have larger sulfur capacity and good regeneration and recycling capability, so that the desulfurizing agent is extremely practical in unloading and regenerating.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a regeneration method capable of recycling the catalyst containing the manganese oxide molecular sieve after absorbing hydrogen sulfide.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A method for regenerating a catalyst comprising a manganese oxide molecular sieve, comprising:
Placing a catalyst containing a manganese oxide molecular sieve after adsorbing hydrogen sulfide in an extraction cavity;
Introducing an organic solvent into the extraction chamber, performing extraction treatment, filtering and drying the obtained product, and then placing the product into a regeneration chamber; and
And introducing oxidizing gas into the regeneration chamber, heating the regeneration chamber to a regeneration temperature, and then maintaining the constant temperature for oxidation regeneration to recover the desulfurization activity of the manganese oxide molecular sieve-containing catalyst.
In some embodiments, the organic solvent is selected from one or more of carbon disulfide, toluene, benzene, and ammonium sulfide.
In some embodiments, the extraction treatment is performed at a temperature of 20 to 200 ℃ for a treatment time of 1 to 12 hours.
In some embodiments, the regeneration temperature is 200-600 ℃, the temperature rise rate of the regeneration temperature is 3-20 ℃/min, and the constant temperature is 1-10h.
In some embodiments, the oxidizing gas comprises one or more of oxygen, carbon dioxide, nitrous oxide.
In some embodiments, the oxidizing gas is introduced before, during, or after the regeneration chamber is warmed to the regeneration temperature.
In some embodiments, the manganese oxide molecular sieve-containing catalyst is a manganese oxide molecular sieve, or the manganese oxide molecular sieve-containing catalyst comprises a manganese oxide molecular sieve and an active component selected from one or more of copper oxide, iron oxide, zinc oxide, titanium oxide, tungsten oxide, zirconium oxide.
In some embodiments, the manganese oxide molecular sieve is selected from one or more of birnessite, bucil, hydromanganese, barium manganese, potassium manganese, and calcium manganese.
In some embodiments, when the manganese oxide molecular sieve-containing catalyst comprises a manganese oxide molecular sieve and an active component, the manganese oxide molecular sieve is present in an amount of from 80 to 99.5 wt% and the active component is present in an amount of from 0.5 to 20 wt% based on the dry weight of the manganese oxide molecular sieve-containing catalyst.
In some embodiments, the copper oxide is copper oxide and/or cuprous oxide, and the iron oxide is selected from one or more of ferrous oxide, ferric oxide, and ferric oxide.
The regeneration method of the invention is simple and easy to implement, has good repeatability, and the regenerated catalyst has stable property, can recover sulfur capacity, reduces the generation of dangerous waste and dangerous solid caused by frequent replacement of the catalyst, can reduce the cost of the desulfurizing agent and the environmental protection cost, and is beneficial to industrialized popularization.
Drawings
FIG. 1 is a reaction scheme of the process for removing hydrogen sulfide in the present invention.
Detailed Description
The technical scheme of the invention is further described below according to specific embodiments. The scope of the invention is not limited to the following examples, which are given for illustrative purposes only and do not limit the invention in any way.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements, etc. with the word "known to those skilled in the art", "prior art", or its synonyms, the word "derived" is intended to cover those conventionally used in the art as the application suggests, but also includes those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present invention, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is understood to be disclosed or described in this invention unless the combination is obviously unreasonable by those skilled in the art. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
The invention provides a method for regenerating a catalyst containing a manganese oxide molecular sieve, which comprises the following steps:
Placing a catalyst containing a manganese oxide molecular sieve after adsorbing hydrogen sulfide in an extraction cavity;
Introducing an organic solvent into the extraction chamber, performing extraction treatment, filtering and drying the obtained product, and then placing the product into a regeneration chamber; and
Oxidizing gas is introduced into the regeneration chamber, the regeneration chamber is heated to a regeneration temperature, and then the constant temperature is maintained for oxidation regeneration.
The regeneration method mainly comprises two steps of extraction and oxidation, wherein the extraction is carried out in an extraction chamber, and the oxidation is carried out in a regeneration chamber. The extraction chamber is a chamber which is convenient for solvent extraction treatment, such as a Soxhlet extractor and the like, and the regeneration chamber can be a separate closed chamber or can be a part of a reactor, namely, oxidation regeneration can be performed in situ in a reaction system for removing hydrogen sulfide.
The catalyst comprising the manganese oxide molecular sieve is first mixed with a solvent in an extraction chamber for extraction treatment, and the solvent used in the present invention is an organic solvent, preferably a nonpolar organic solvent, such as one or more selected from carbon disulphide, toluene, benzene and ammonium sulphide.
The extraction treatment temperature is normal temperature-200 ℃, for example 20-200 ℃, and the treatment time is 1-12h as long as the solvent can realize reflux.
The extraction treatment can remove impurities on the surface of the desulfurized catalyst, so that the active center is exposed and convenient to regenerate.
After the extraction treatment is finished, the product is filtered and dried, for example, the product is dried for 12 hours at 120 ℃, and the dried material is placed into a regeneration chamber for subsequent oxidation treatment.
The oxidation treatment comprises introducing an oxidizing gas into the regeneration chamber, heating the regeneration chamber to a regeneration temperature, and then maintaining the constant temperature for oxidation regeneration. The regeneration temperature is 200-600 ℃, the heating rate is 3-20 ℃/min, preferably 5-15 ℃/min, and the constant temperature time is 1-10h, preferably 2-8h.
The oxidizing gas introduced into the regeneration chamber comprises one or more of oxygen, carbon dioxide and nitrous oxide, and can also comprise nitrogen, wherein the volume concentration of the oxygen-containing element is 0.1-30%. The oxidizing gas is introduced before, during, or after the regeneration chamber is warmed to the regeneration temperature.
The subsequent constant temperature treatment is carried out in an oxidizing atmosphere, and the S atoms in the catalyst can be replaced by O atoms so as to restore the desulfurization activity.
The catalyst of the manganese oxide-containing molecular sieve after adsorbing hydrogen sulfide is preferably a catalyst for adsorbing saturated manganese oxide-containing molecular sieve.
The catalyst comprising the manganese oxide molecular sieve may be a manganese oxide molecular sieve prior to adsorption of hydrogen sulfide, or the catalyst comprising the manganese oxide molecular sieve may comprise a manganese oxide molecular sieve and an active component.
The manganese oxide molecular sieve used in the invention is one or more selected from birnessite (delta-MnO 2), bucholite, hydromanganese ore (MnO 2·nH2 O), manganese barium ore (OMS-6), manganese potassium ore (OMS-2) and calomel ore (OMS-1), has a special crystal structure, and can realize purification of hydrogen sulfide through adsorption and catalytic conversion. Specifically, the manganese oxide molecular sieve is an alkaline molecular sieve, and the alkaline makes the manganese oxide molecular sieve and the acidic hydrogen sulfide combine very easily, so that the manganese oxide molecular sieve is suitable for adsorbing the acidic hydrogen sulfide due to the huge specific surface area and the proper pore diameter. Besides hydrogen sulfide, the basic structural unit of the molecular sieve can also react with hydrogen sulfide to generate manganese sulfide, so that the sulfur capacity of the catalyst is increased. Because of its special crystal structure, the manganese oxide molecular sieve can achieve purification of hydrogen sulfide by a combination of adsorption and catalytic conversion.
The manganese oxide molecular sieve used in the invention is prepared by hydrothermal synthesis reaction, the hydrothermal reaction can be carried out in a reaction kettle or in a flask by a reflux method, and the specific steps can be as follows:
carrying out hydrothermal synthesis reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound, collecting a solid product, washing, drying and roasting to obtain the manganese oxide molecular sieve.
The temperature of the hydrothermal synthesis reaction is 60-200 ℃ and the reaction time is 1-36h.
Before the hydrothermal synthesis reaction, acid may be added to the aqueous solution to adjust the pH value of the aqueous solution to 0.2-3, so as to facilitate crystal growth. The acid for adjusting the pH of the solution may be any acid, such as nitric acid, hydrochloric acid, sulfuric acid, acetic acid, etc., preferably nitric acid.
The manganese compounds in the oxidized state and the manganese compounds in the reduced state of the present invention are relatively speaking; the manganese compound in an oxidation state generally refers to a compound containing manganese in a relatively high valence state (such as Mn 7+、Mn6+, etc.), and for example, can be one or more selected from potassium permanganate, potassium manganate and sodium permanganate; the reduced manganese compound generally refers to a compound containing relatively low valence manganese (e.g., mn 2+, etc.), and may be selected from one or more of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride, for example.
In order to achieve the desired effect, the molar ratio of the manganese compound in an oxidized state to the manganese compound in a reduced state may be (0.2 to 3): 1.
After the solid product is obtained, washing, drying and roasting are carried out, wherein washing means that the collected solid product is washed by deionized water until the washing liquid is neutral (for example, the pH value is 6.5-7.5). Washing is followed by drying, and the drying conditions may include: the temperature is 80-350 ℃, preferably 100-300 ℃; the time is 1 to 24 hours, preferably 2 to 12 hours. And then roasting, wherein the roasting conditions can include: the temperature is 200-900 ℃, preferably 250-800 ℃; the time is 0.5 to 12 hours, preferably 2 to 6 hours, and the calcination can be performed in an air atmosphere. Through the steps, the manganese oxide molecular sieve can be prepared.
When the manganese oxide molecular sieve-containing catalyst comprises a manganese oxide molecular sieve and an active component, the active component is selected from one or more of copper oxide, iron oxide, zinc oxide, titanium oxide, tungsten oxide and zirconium oxide, the copper oxide can be copper oxide, cuprous oxide or a mixture of copper oxide and cuprous oxide, and the iron oxide is selected from one or more of ferrous oxide, ferric oxide and ferroferric oxide.
The content of the manganese oxide molecular sieve is 80 to 99.5 weight percent and the content of the active component is 0.5 to 20 weight percent based on the dry weight of the catalyst containing the manganese oxide molecular sieve.
The manganese oxide molecular sieve-containing catalyst may also include copper manganese ore (CuMn 2O4), the copper manganese ore crystals may further increase sulfur capacity.
The catalyst comprising the manganese oxide molecular sieve and the active component can be prepared by a doping method or a loading method, and both comprise hydrothermal reaction, and can be carried out in a reaction kettle or in a flask by a reflux method.
For doping method, the reduced manganese compound is mixed with the active metal salt, and then mixed with the oxidized manganese compound for hydrothermal reaction, so as to avoid that the active metal salt and the oxidized manganese compound form an undesirable complex to change the crystal structure, the specific steps can include:
dissolving a reduced manganese compound and an active metal salt in water to obtain a mixed solution,
And mixing the manganese oxide compound with the mixed solution, performing hydrothermal reaction, collecting precipitate, drying and roasting the precipitate to obtain the catalyst.
For the loading method, firstly preparing the manganese oxide molecular sieve from the manganese compound in the oxidation state and the manganese compound in the reduction state, and then loading the active metal salt on the manganese oxide molecular sieve, the method specifically comprises the following steps:
Carrying out hydrothermal reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound, collecting a solid product, and washing, drying and roasting to obtain a manganese oxide molecular sieve;
And loading the active metal salt onto a manganese oxide molecular sieve, and drying and roasting to obtain the catalyst.
In order to achieve the desired effect, the molar ratio of the manganese compound in an oxidized state, the manganese compound in a reduced state and the active metal salt may be (0.2 to 3): 1: (0.01-1).
The active metal salt used in the present invention is selected from one or more of nitrate, sulfide salt, chloride salt, citrate, acetate, for example, copper nitrate, copper sulfide, copper chloride, iron nitrate, iron sulfide, iron chloride, iron citrate, iron acetate, etc., preferably an active metal salt having high solubility in water.
After the precipitate or solid product is obtained, washing, drying and roasting are carried out, wherein washing means that the collected solid product is washed by deionized water until the washing liquid is neutral (for example, the pH value is 6.5-7.5). Washing is followed by drying, and the drying conditions may include: the temperature is 80-350 ℃, preferably 100-300 ℃; the time is 1 to 24 hours, preferably 2 to 12 hours. And then roasting, wherein the roasting conditions can include: the temperature is 200-900 ℃, preferably 250-800 ℃; the time is 0.5 to 12 hours, preferably 2 to 6 hours, and the calcination may be performed under an air atmosphere or under an inert gas atmosphere, preferably under an N 2 atmosphere.
After loading the active metal salt onto the manganese oxide molecular sieve, drying and roasting the manganese oxide molecular sieve again to prepare the catalyst, wherein the drying temperature is 80-350 ℃, the time is 1-24 h, the roasting temperature is 200-900 ℃, and the time is 0.5-12 h.
Before the hydrothermal synthesis reaction, acid may be added to the solution to adjust the pH value of the solution to 0.2-3, so as to facilitate crystal growth. The acid for adjusting the pH of the solution may be any acid, such as nitric acid, hydrochloric acid, sulfuric acid, acetic acid, etc., preferably nitric acid.
The hydrothermal reaction temperature is generally controlled to be 80-200 ℃, and in the doping method, the hydrothermal reaction temperature can be adjusted to be 150-200 ℃, so that the crystal structure of the manganese oxide molecular sieve is formed and copper-manganese ore (CuMn 2O4) is also formed.
The catalyst of the manganese oxide-containing molecular sieve has the characteristics of high desulfurization precision, high sulfur capacity and high single-pass conversion rate, and can comprise the following steps when used for the reaction of removing hydrogen sulfide:
placing a catalyst containing a manganese oxide molecular sieve in a reactor; and
And introducing a reaction gas containing hydrogen sulfide into the reactor to perform a hydrogen sulfide removal reaction so as to enable the catalyst containing the manganese oxide molecular sieve to adsorb and convert the hydrogen sulfide.
The treated reaction gas containing hydrogen sulfide may include hydrogen, and further may include nitrogen or other inert gases, and the concentration of hydrogen sulfide in the reaction gas is 0.1 to 3% by volume.
The reactor used is preferably a fixed bed reactor so that the reaction gas containing hydrogen sulfide is passed continuously.
When the reaction of removing hydrogen sulfide is carried out, the temperature in the reactor is normal temperature to 200 ℃, the pressure is normal pressure, and the volume airspeed of the reaction is 500 to 20000h -1.
By carrying out the hydrogen sulfide removal reaction on the regenerated catalyst containing the manganese oxide molecular sieve again, the following steps can be obtained: after the regeneration treatment, sulfur element in the catalyst is removed, metal sulfide is replaced by metal oxide by oxidizing atmosphere, and the crystal structure of the manganese oxide molecular sieve is recovered, so that the catalyst shows better desulfurization activity and sulfur capacity when being desulfurized again.
The regeneration method of the invention is simple and easy to implement, has good repeatability, and the regenerated catalyst has stable property, can recover sulfur capacity, reduces the generation of dangerous waste and dangerous solid caused by frequent replacement of the catalyst, can reduce the cost of the desulfurizing agent and the environmental protection cost, and is beneficial to industrialized popularization.
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the preferred embodiments and not limiting of the invention, and any equivalent examples of equivalent variations are possible by those skilled in the art using the teachings set forth above.
Examples
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the present invention are analytically pure and commercially available.
The H 2 S analyzer used in the invention is a German SICK GMS810 hydrogen sulfide analyzer.
Preparation example 1
3.17G of potassium permanganate is dissolved in 40.55g of deionized water, heated and stirred to be dissolved to form a potassium permanganate solution, the potassium permanganate solution is mixed with 5.78g of 50 wt% manganese sulfate solution, 6ml of nitric acid is added to adjust the pH value of the solution to 1.0, and the solution is reacted at 130 ℃ for 24 hours after uniform stirring.
The resulting brown precipitate was filtered and washed with deionized water several times until ph=7 of the washing solution, and then the solid product was dried overnight at 120 ℃, and then calcined for 4 hours in an air atmosphere at 400 ℃ to prepare a manganese oxide molecular sieve, namely catalyst C1 containing a manganese oxide molecular sieve: OMS-2.
Preparation example 2
3.17G of potassium permanganate is dissolved in 40.55g of deionized water, the solution is heated and stirred to form a potassium permanganate solution, 5.78g of 50 wt% manganese sulfate solution and 1.22g of copper nitrate are mixed and stirred uniformly, the two solutions are mixed, 6ml of nitric acid is added and stirred uniformly, and the mixture is reacted for 24 hours at 130 ℃.
The brown precipitate formed was filtered and washed with deionized water several times until the ph=7 of the washing solution, and then the solid product was dried overnight at 120 ℃ and calcined at 400 ℃ for 4 hours to produce catalyst C2 containing a manganese oxide molecular sieve: 3% CuO-OMS-2.
Preparation example 3
3.17G of potassium permanganate is dissolved in 40.55g of deionized water, the solution is heated and stirred to form potassium permanganate solution, 5.78g of 50 wt% manganese sulfate solution and 1.56g of ferric nitrate are mixed and stirred uniformly, 6ml of nitric acid is added to mix uniformly, and then the mixture is reacted for 24 hours at 130 ℃.
The brown precipitate formed was filtered and washed several times with deionized water to ph=7 of the washing solution, and then the solid product was dried overnight at 120 ℃ and calcined in air at 500 ℃ for 4 hours to produce catalyst C3 containing a manganese oxide molecular sieve: 10% Fe 2O3 -OMS-2.
FIG. 1 is a reaction flow chart of the method for removing hydrogen sulfide in the invention, and as shown in FIG. 1, catalysts of manganese oxide-containing molecular sieves of preparation examples 1 to 3 are used for a gas phase hydrogen sulfide removal test, and the specific steps of the reaction are as follows:
The catalyst containing manganese oxide molecular sieve of preparation examples 1-3 was weighed 1.5g respectively, placed in a fixed bed reactor, and then mixed gas with a molar concentration of 0.5% H 2S-H2 was introduced into the fixed bed reactor together with N 2 after passing through MFC (mass flow meter), and reacted at 150℃under normal pressure, the volume space velocity of the reaction was 2250h -1.
In the reaction process, an H 2 S analyzer is used for detecting the real-time concentration of the hydrogen sulfide, and when the concentration of the hydrogen sulfide reaches 100ppm, the bed layer is considered to be penetrated, and the hydrogen sulfide remover reaches saturated adsorption.
The reacted mixed gas is introduced into a tail gas absorption tank, and can be further treated or exhausted after being tested to meet the environmental protection requirement.
The sulfur capacity of the catalyst was calculated based on the mass of hydrogen sulfide actually adsorbed in the reaction, and the reaction results are shown in Table 1. The catalyst C1 of preparation example 1 was saturated with hydrogen sulfide and then was designated as C1-B, the catalyst C2-B was saturated with hydrogen sulfide, and the catalyst C3-B was saturated with hydrogen sulfide.
After saturation of the adsorption of the manganese oxide molecular sieve-containing catalyst of preparation examples 1-3, regeneration was carried out and the dehydrosulfide test was carried out again using the method provided by the present invention.
Example 1
Placing the C1-B catalyst in a Soxhlet extractor, heating to 80 ℃ for extraction treatment for 5 hours by taking carbon disulfide as a solvent, filtering the catalyst after extraction, and drying at 120 ℃ for 12 hours.
The dried catalyst is placed in a reactor again for oxidation treatment with 1%O 2-N2, and is heated to 400 ℃ at 10 ℃/min for 3 hours until the regeneration is finished.
After regeneration, the catalyst is reused for the reaction of removing hydrogen sulfide, and when the concentration of hydrogen sulfide in the tail gas reaches 100ppm, the catalyst is considered to penetrate through the bed layer, and the catalyst reaches saturated adsorption. The sulfur capacity of the catalyst was calculated based on the mass of hydrogen sulfide actually adsorbed in the reaction, and the reaction results are shown in Table 1.
Example 2
The C1-B catalyst was regenerated in the same manner as in example 1 except that the extraction solvent and the extraction treatment temperature were different, and an ammonium sulfide solution having a concentration of 15% was selected as the extraction solvent, and the reaction results were shown in Table 1, followed by extraction at 100℃for 5 hours.
Example 3
The C2-B catalyst was regenerated in the same manner as in example 1 except that the extraction solvent used and the extraction treatment temperature were different, toluene was selected as the extraction solvent, and extraction was carried out at 100℃for 5 hours, and the reaction results are shown in Table 1.
Example 4
The C3-B catalyst was regenerated in the same manner as in example 1 except that the extraction solvent used and the extraction treatment temperature were different, benzene was selected as the extraction solvent, extraction was carried out at 100℃for 5 hours, and the reaction results are shown in Table 1.
Comparative example 1
The C1-B catalyst was treated in the reaction system directly with 5% O 2-N2 at 400℃for 2h and then used again in the dehydrosulphide test, the reaction results being given in Table 1.
TABLE 1 dehydrosulfuration test reaction results
As can be seen from the test results in Table 1, after the catalyst containing the manganese oxide molecular sieve is regenerated by the regeneration method of the invention, the sulfur capacity is obviously higher than that of the comparative example when the catalyst is reused in the hydrogen sulfide removal reaction, which shows that most of sulfur elements in the catalyst are removed after the regeneration treatment, the metal sulfide is replaced by the metal oxide by the oxidizing atmosphere, and the crystal structure of the manganese oxide molecular sieve is recovered, so that the catalyst shows better desulfurization activity and sulfur capacity when the catalyst is desulfurized again.
In conclusion, the regeneration method disclosed by the invention is simple and easy to implement, good in repeatability, stable in catalyst property after regeneration, recoverable in sulfur capacity, capable of reducing the generation of dangerous waste and dangerous solid caused by frequent replacement of the catalyst, capable of reducing the cost of the desulfurizing agent and the environmental protection cost, and beneficial to industrialized popularization.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for regenerating a catalyst containing a manganese oxide molecular sieve, characterized in that the regeneration method consists of two steps of extraction and oxidation, wherein the extraction is performed in an extraction chamber and the oxidation is performed in a regeneration chamber;
the catalyst of the manganese oxide-containing molecular sieve is a catalyst of the manganese oxide-containing molecular sieve after absorbing hydrogen sulfide;
The regeneration method comprises the following steps:
Placing a catalyst containing a manganese oxide molecular sieve after adsorbing hydrogen sulfide in an extraction cavity;
Introducing an organic solvent into the extraction chamber, performing extraction treatment, filtering and drying the obtained product, and then placing the product into a regeneration chamber; and
Introducing oxidizing gas into the regeneration chamber, heating the regeneration chamber to a regeneration temperature, and then maintaining a constant temperature for oxidation regeneration to recover the desulfurization activity of the manganese oxide molecular sieve-containing catalyst;
The catalyst of the manganese oxide-containing molecular sieve is a manganese oxide molecular sieve, or the catalyst of the manganese oxide-containing molecular sieve comprises a manganese oxide molecular sieve and an active component.
2. The regeneration process according to claim 1, characterized in that the organic solvent is selected from one or more of carbon disulphide, toluene, benzene and ammonium sulphide.
3. The regeneration method according to claim 1, wherein the extraction treatment is carried out at a temperature of 20 to 200 ℃ for a treatment time of 1 to 12 hours.
4. The regeneration method according to claim 1, wherein the regeneration temperature is 200-600 ℃, the temperature rising rate of the regeneration temperature is 3-20 ℃/min, and the constant temperature is 1-10h.
5. The regeneration method according to claim 1, wherein the oxidizing gas comprises one or more of oxygen, carbon dioxide, nitrous oxide.
6. The regeneration method according to claim 1, wherein the oxidizing gas is introduced before, during or after the regeneration chamber is warmed to the regeneration temperature.
7. The regeneration method according to any one of claims 1 to 6, wherein the active component is selected from one or more of copper oxide, iron oxide, zinc oxide, titanium oxide, tungsten oxide, zirconium oxide.
8. The regeneration method according to claim 7, wherein the manganese oxide molecular sieve is selected from one or more of birnessite, bucer ore, hydromanganese ore, barium manganese ore, potassium manganese ore, and calcium manganese ore.
9. The regeneration method according to claim 7, wherein when the manganese oxide molecular sieve-containing catalyst comprises a manganese oxide molecular sieve and an active component, the manganese oxide molecular sieve is contained in an amount of 80 to 99.5% by weight and the active component is contained in an amount of 0.5 to 20% by weight, based on the dry weight of the manganese oxide molecular sieve-containing catalyst.
10. The method according to claim 7, wherein the copper oxide is copper oxide and/or cuprous oxide, and the iron oxide is one or more selected from ferrous oxide, ferric oxide and ferric oxide.
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| CN106179489A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The renovation process of decaying catalyst |
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| US10081006B2 (en) * | 2014-12-17 | 2018-09-25 | University Of Connecticut | Adsorptive desulfurization |
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| CN106179489A (en) * | 2015-04-29 | 2016-12-07 | 中国石油化工股份有限公司 | The renovation process of decaying catalyst |
| CN109475842A (en) * | 2016-06-30 | 2019-03-15 | 巴斯夫公司 | For removing the oxidation manganese-based catalyst and catalyst-assembly of formaldehyde and volatile organic compounds |
| CN109847730A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of regeneration method of desulfuration adsorbent |
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