CN115779923A - Desulfurization and denitrification catalyst, and preparation method and application thereof - Google Patents
Desulfurization and denitrification catalyst, and preparation method and application thereof Download PDFInfo
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- CN115779923A CN115779923A CN202111055151.3A CN202111055151A CN115779923A CN 115779923 A CN115779923 A CN 115779923A CN 202111055151 A CN202111055151 A CN 202111055151A CN 115779923 A CN115779923 A CN 115779923A
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- metal component
- noble metal
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- inorganic oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 173
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 52
- 230000023556 desulfurization Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 135
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 69
- 239000011159 matrix material Substances 0.000 claims abstract description 62
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003546 flue gas Substances 0.000 claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 38
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims description 124
- 239000000203 mixture Substances 0.000 claims description 76
- 229910052751 metal Inorganic materials 0.000 claims description 71
- 239000002184 metal Substances 0.000 claims description 71
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 56
- 239000011265 semifinished product Substances 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 239000012265 solid product Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 229910052763 palladium Inorganic materials 0.000 claims description 28
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 27
- 239000001099 ammonium carbonate Substances 0.000 claims description 27
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 238000000975 co-precipitation Methods 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052596 spinel Inorganic materials 0.000 claims description 7
- 239000011029 spinel Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 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
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 239000010451 perlite Substances 0.000 claims description 3
- 235000019362 perlite Nutrition 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 71
- 238000005303 weighing Methods 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 238000003756 stirring Methods 0.000 description 34
- 239000008367 deionised water Substances 0.000 description 32
- 229910021641 deionized water Inorganic materials 0.000 description 32
- 239000004005 microsphere Substances 0.000 description 18
- 238000000967 suction filtration Methods 0.000 description 18
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 238000000227 grinding Methods 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 229940024548 aluminum oxide Drugs 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 9
- 239000011565 manganese chloride Substances 0.000 description 9
- 229940099607 manganese chloride Drugs 0.000 description 9
- 235000002867 manganese chloride Nutrition 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 229910001960 metal nitrate Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 239000012696 Pd precursors Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- -1 magnesium aluminate Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 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
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910001682 nordstrandite Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention relates to the technical field of catalyst preparation, and discloses a desulfurization and denitrification catalyst, and a preparation method and application thereof. The desulfurization and denitrification catalyst comprises the following components in percentage by weight based on the total weight of the catalyst, in terms of oxides: 25-92wt% of inorganic oxide matrix, 6-70wt% of rare earth metal component, 1-12wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-10wt% of non-noble metal component selected from VIIB group; calculated by elements:0.01-1.5wt% of noble metal component. The preparation method of the desulfurization and denitrification catalyst provided by the invention is simple to operate and easy to realize, and can effectively reduce SO in catalytic cracking regenerated flue gas x And NO x And (4) discharging.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a desulfurization and denitrification catalyst and a preparation method and application thereof.
Background
During the catalytic cracking reaction, the cracking activity of the catalyst is reduced due to carbon deposition on the surface of the catalyst. To restore the cracking activity of the catalyst and to provide the required heat, regeneration must be carried out under oxygen-containing conditions to burn off most of the coke in the internal and external surfaces of the catalyst. The high temperature and oxygen-rich environment accompanied with the burning of the catalyst can generate SO x And NO x And the like, and the emission limit of the smoke pollutants is more and more strict on the global scale.
The main technical measures for reducing the emission of catalytic cracking regeneration flue gas pollutants at present comprise: the regenerator is optimized, and an auxiliary agent and flue gas post-treatment are used, wherein the method for adding the auxiliary agent does not need extra equipment investment cost, and the operation is flexible. At present, flue gas environmental protection additives such as denitration additives, sulfur transfer agents and the like all take single flue gas pollutants as removal targets. For example: CN104399478A discloses a sulfur transfer agent and preparation and evaluation methods thereof, which are used for removing SO from catalytic cracking flue gas x . CN101311248B provides a catalyst capable of reducing NO in catalytic cracking regeneration flue gas x Composition for reducing NO in catalytically cracked flue gas x 。
The above patent documents separately remove SO from the regeneration flue gas x And NO x When the method is used, the method has a good removal effect, but can not remove the nitrogen oxides and the sulfur oxides simultaneously. This results in simultaneous removal of SO if desired x And NO x The total amount of the auxiliary agent required is large. This aspect increases the smokeThe cost for removing the pollutants, and on the other hand, the distribution of the products of catalytic cracking can be influenced by more additive filling amount.
Disclosure of Invention
The invention aims to overcome the defects that the existing desulfurization and denitrification technology cannot simultaneously remove nitrogen oxides and sulfur oxides and is high in cost, and provides a desulfurization and denitrification catalyst and a preparation method and application thereof. The invention provides a method for reducing SO x And NO x The discharged desulfurization and denitrification catalyst composition has high activity for removing pollutants, the preparation method is simple, and SO in catalytic cracking regeneration flue gas can be effectively reduced x And NO x And (4) discharging.
In order to achieve the above object, the first aspect of the present invention provides a desulfurization and denitrification catalyst comprising, in weight percent based on the total weight of the catalyst,
calculated by oxide: 25-92wt% of inorganic oxide matrix, 6-70wt% of rare earth metal component, 1-12wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-10wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.01-1.5wt% of noble metal component.
Preferably, the catalyst comprises, in weight percent based on the total weight of the catalyst,
calculated by oxide: 40-85wt% of inorganic oxide matrix, 12-60wt% of rare earth metal component, 2-10wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-8wt% of non-noble metal component selected from VIIB group;
calculated by elements: noble metal component 0.02-1.2wt%;
preferably, the catalyst comprises, in weight percent based on the total weight of the catalyst,
calculated by oxide: 45-80wt% of inorganic oxide matrix, 12-48wt% of rare earth metal component, 2-8wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 2-5wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.02-1.0wt% of noble metal component.
By adopting the technical scheme, different types of metals are selected to cooperate in a specific content range, so that the different types of metals can play a synergistic effect, the consumption of noble metals can be reduced, and the cost is reduced.
Meanwhile, the desulfurization and denitrification catalyst provided by the invention has good effect of simultaneously removing SO in flue gas x And NO x Within 0.5h, in the presence of SO x And NO x In the reaction of (1), the desulfurization and denitrification catalyst is used for NO x The total conversion rate reaches 34-87%, for example, 78%, 53%, 61%, 87%, 43%, 34%, 72%, 67%, and the desulfurization and denitrification catalyst pair SO x Total conversion reaches 28-65%, e.g., 53%, 28%, 46%, 65%, 47%, 38%, 51%; in 1.5h, SO is mixed in x And NO x In the reaction of (2), the desulfurization and denitrification catalyst is used for NO x The total conversion rate reaches 26-61%, for example, 55%, 39%, 44%, 61%, 32%, 26%, 51%, 48%, and the desulfurization and denitrification catalyst pair SO x The overall conversion reaches 19-39%, e.g., 33%, 19%, 29%, 39%, 30%, 25%, 31%, 32%.
Preferably, the rare earth metal component is selected from one or a mixture of lanthanum, cerium, praseodymium and neodymium, and more preferably lanthanum.
The non-noble metal component of one or more of VB, VIII, IB and IIB groups is selected from one or more of mixture of iron, cobalt, nickel, copper, zinc and vanadium, and cobalt is more preferable.
The non-noble metal component in the VIIB group is manganese.
The noble metal component is selected from one or a mixture of more of ruthenium, rhodium, rhenium, platinum, palladium, silver, iridium and gold, more preferably one or a mixture of more of platinum, palladium and rhodium, and most preferably palladium.
By adopting the technical scheme, proper rare earth metal components, non-noble metal components and noble metal components are selected, SO that the components are mutually cooperated to realize simultaneous removal of SO in the flue gas x And NO x The effect of (1).
The second aspect of the present invention provides a preparation method of a desulfurization and denitrification catalyst, comprising the following steps:
s1, preparing an active metal precursor: adopting a coprecipitation method or a sol-gel method;
s2, preparing a catalyst semi-finished product: mixing and pulping an active metal precursor, an inorganic oxide matrix and/or a precursor of the inorganic oxide matrix and optionally a precursor of a noble metal component to obtain a slurry, and drying and roasting the slurry;
the method also optionally includes: s3, taking a solution containing a precursor of a noble metal component as an impregnation solution, impregnating the semi-finished product of the catalyst obtained in the step S2 to obtain a solid product, and drying and roasting the solid product;
wherein, the active metal in the active metal precursor comprises rare earth metal components, one or more non-noble metal components selected from VB, VIII, IB and IIB groups and VIIB group non-noble metal components;
the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the precursor of the noble metal component are used in such amounts that the prepared catalyst comprises the following components in percentage by weight based on the total weight of the catalyst: 25-92wt% of inorganic oxide matrix, 6-70wt% of rare earth metal component, 1-12wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB, and 1-10wt% of non-noble metal component selected from VIIB; calculated by elements: 0.01-1.5wt% of noble metal component.
Through the technical scheme, the method for removing SO in flue gas simultaneously is prepared x And NO x The preparation method of the desulfurization and denitrification catalyst is simple to operate, easy to realize, low in cost and beneficial to industrial production.
The third aspect of the invention provides an application of the desulfurization and denitrification catalyst.
Preferably, the desulfurization and denitrification catalyst is mixed with SO x And NO x Contacting the flue gas;
wherein SO is removed x And NO x The conditions of (a) are as follows: temperature of500-800 deg.C, 0.02-4MPa, and the volume space velocity of flue gas is 100-50000h -1 ；
Preferably, SO in the flue gas x In an amount of 0.001-0.5 vol%, NO x The content of (B) is 0.001-0.3 vol%.
By adopting the technical scheme, the desulfurization and denitrification catalyst prepared by the invention is applied to the removal of SO in flue gas (preferably catalytic cracking regenerated flue gas) x And NO x For SO in flue gas x And NO x Has excellent removal effect and realizes the purpose of removing the two simultaneously.
In conclusion, the catalyst provided by the invention can effectively reduce SO in flue gas x And NO x Emissions, presumably due to: the introduction of the trace precious metal changes the geometric electronic structure of other metal oxide compositions in the desulfurization and denitrification catalyst, greatly improves the redox capability of the catalyst, and is favorable for promoting SO x Oxidation and NO x Reduction; on the basis, the introduction of the VIIB non-noble metal component ensures that the surface of the catalyst is rich in more oxygen vacancies, and improves the NO ratio of the catalyst x The decomposition ability of (c). In addition, the preparation method provided by the invention is simple to operate and easy to realize, and can effectively reduce SO in catalytic cracking regeneration flue gas x And NO x During which the dissociated NO is adsorbed by the catalyst x Can promote SO x Conversion to sulfate, thereby achieving simultaneous removal of SO x And NO x The purpose of (1).
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a desulfurization and denitrification catalyst, which comprises the following components in percentage by weight based on the total weight of the catalyst,
calculated by oxide: 25-92wt% of inorganic oxide matrix, 6-70wt% of rare earth metal component, 1-12wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-10wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.01-1.5wt% of noble metal component.
According to the present invention, it is preferable to include, in weight percent based on the total weight of the catalyst,
calculated by oxide: 40-85wt% of inorganic oxide matrix, 12-60wt% of rare earth metal component, 2-10wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-8wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.02-1.2wt% of noble metal component.
More preferably, the catalyst comprises, in weight percent based on the total weight of the catalyst,
calculated by oxide: 45-80wt% of inorganic oxide matrix, 12-48wt% of rare earth metal component, 2-8wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 2-5wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.02-1.0wt% of noble metal component;
most preferably, the catalyst comprises, in weight percent based on the total weight of the catalyst,
calculated by oxide: 50-80wt% of inorganic oxide matrix, 12-43wt% of rare earth metal component, 2-5wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 2-5wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.02-0.05wt% of noble metal component.
By adopting the technical scheme, different types of metals are selected to cooperate in a specific content range, so that the different types of metals can play a synergistic effect, the consumption of noble metals can be reduced, and the cost is reduced.
According to the inventionThe presence of a rare earth metal component may be used in the present invention to further enhance the SO removal of the catalyst x With NO x Preferably, the rare earth metal component is one or more selected from lanthanum, cerium, praseodymium and neodymium, and more preferably lanthanum.
In one embodiment, the group VB non-noble metal component may be selected from one or a mixture of vanadium, niobium and tantalum; the non-noble group VIII metal component may be selected from one or a mixture of iron, cobalt and nickel; the group IB non-noble metal component may be copper; the group IIB non-noble metal component can be selected from one or a mixture of zinc, cadmium and mercury.
In a preferred embodiment, the non-noble metal component of one or more of groups VB, VIII, IB, IIB is selected from the group consisting of mixtures of one or more of iron, cobalt, nickel, copper, zinc and vanadium, more preferably cobalt.
In a preferred embodiment, the group VIIB non-noble metal component is manganese.
In a preferred embodiment, the noble metal component is selected from the group consisting of ruthenium, rhodium, rhenium, platinum, palladium, silver, iridium and gold, more preferably from the group consisting of platinum, palladium and rhodium, and most preferably palladium.
According to the desulfurization and denitrification catalyst prepared by the method, the inorganic oxide matrix is various inorganic oxide matrices commonly used in the field, such as one or a mixture of more of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite. In the present invention, the spinel is various spinels conventionally used in the art, such as one or a mixture of more of magnesium aluminate spinel, zinc aluminate spinel and titanium aluminate spinel.
In a preferred embodiment according to the invention, the inorganic oxide substrate is alumina.
In a preferred embodiment, the alumina is selected from one or more of γ -alumina, δ -alumina, η -alumina, ρ -alumina, κ -alumina and χ -alumina, which are not particularly limited in the present invention.
In a preferred embodiment of the present invention, the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB is (0.6-18): 1, more preferably (2-12): 1, and still more preferably (3-6): 1, calculated as the metal element.
According to a particularly preferred embodiment of the invention, 50 to 80 wt.% of alumina, 12 to 43 wt.% of lanthanum, 2 to 5 wt.% of cobalt, 2 to 5 wt.% of manganese, calculated as oxides, in weight percent, based on the total weight of the catalyst; 0.02-0.05wt% of palladium calculated by element; more preferably, the molar ratio of lanthanum to cobalt is (3-6): 1.
The inventor of the present invention finds in the research process that, under a particularly preferred embodiment, at least one of rare earth metal element lanthanum and non-noble metal element containing cobalt and manganese and noble metal element are selected as active components, and the active components are applied to the desulfurization and denitrification catalyst to effectively reduce NO in flue gas x And SO x And (5) discharging. The inventors speculate that the reason may be due to: the introduction of micro noble metal changes the geometric electronic structure of the metal oxide composition, greatly improves the oxidation-reduction capability of the metal oxide composition, and is favorable for promoting SO x Oxidation and NO of x Reduction of (2); on the basis of this, introduction of p-NO x Manganese with good decomposition capability, so that the surface of the desulfurization and denitrification catalyst is rich in more oxygen vacancies, thereby improving the effect of removing NO from the desulfurization and denitrification catalyst at the same time x And SO x The ability of the cell to perform.
The second aspect of the present invention provides a preparation method of a desulfurization and denitrification catalyst, comprising the following steps:
s1, preparing an active metal precursor: adopting a coprecipitation method or a sol-gel method;
s2, preparing a catalyst semi-finished product: mixing and pulping an active metal precursor, an inorganic oxide matrix and/or a precursor of the inorganic oxide matrix and optionally a precursor of a noble metal component to obtain a slurry, and drying and roasting the slurry;
the method also optionally includes: s3, taking a solution containing a precursor of a noble metal component as an impregnation solution, impregnating the semi-finished product of the catalyst obtained in the step S2 to obtain a solid product, and drying and roasting the solid product;
wherein, the active metal in the active metal precursor comprises rare earth metal components, one or more non-noble metal components selected from VB, VIII, IB and IIB groups and VIIB group non-noble metal components;
the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the noble metal component precursor are used in such amounts that the prepared catalyst comprises the following components in percentage by weight based on the total weight of the catalyst: 25-92wt% of inorganic oxide matrix, 6-70wt% of rare earth metal component, 1-12wt% of one or more non-noble metal components selected from VB, VIII, IB and IIB, and 1-10wt% of non-noble metal component selected from VIIB; calculated by elements: 0.01-1.5wt% of noble metal component.
According to the present invention, preferably, the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the noble metal component precursor are used in such amounts that the catalyst obtained comprises, in percent by weight, based on the total weight of the catalyst, in terms of oxides: 40-85wt% of inorganic oxide matrix, 12-60wt% of rare earth metal component, 2-10wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-8wt% of non-noble metal component selected from VIIB group; calculated by elements: noble metal component 0.02-1.2wt%;
preferably, the active metal precursor, the inorganic oxide matrix and/or precursor of the inorganic oxide matrix, and the noble metal component precursor are used in amounts such that the resulting catalyst comprises, in weight percent, based on the total weight of the catalyst,
calculated by oxide: 45-80wt% of inorganic oxide matrix, 12-48wt% of rare earth metal component, 2-8wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 2-5wt% of non-noble metal component selected from VIIB group;
calculated by elements: noble metal component 0.02-1.0wt%;
most preferably, the active metal precursor, inorganic oxide matrix and/or precursor for an inorganic oxide matrix, and noble metal component precursor are used in amounts such that the resulting catalyst comprises, in weight percent based on the total weight of the catalyst,
calculated by oxide: 50-80wt% of inorganic oxide matrix, 12-483wt% of rare earth metal component, 2-5wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB groups, and 2-5wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.02-0.05wt% of noble metal component.
Preferably, the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB in the active component precursor is (0.6-18): 1, more preferably (2-12): 1, and even more preferably (3-6): 1.
In the preparation method provided by the invention, the selection range of the specific types of the rare earth metal component, one or more non-noble metal components selected from VB, VIII, IB and IIB groups, the non-noble metal component of VIIB group, the noble metal component and the inorganic oxide matrix is as described in the first aspect above, and is not described in detail here.
The preparation method provided by the invention can adopt a coprecipitation method, can also adopt a sol-gel method, and more preferably adopts the coprecipitation method. In the step S1, an active metal precursor is obtained by adopting a coprecipitation method;
preferably, the co-precipitation method comprises:
s11, preparing a first solution containing a rare earth metal component precursor, one or more non-noble metal component precursors selected from VB, VIII, IB and IIB groups and a VIIB non-noble metal component precursor;
s12, carrying out coprecipitation reaction on the first solution and a coprecipitator;
and S13, drying and roasting a solid product obtained by the coprecipitation reaction.
In the present invention, the method for obtaining the first solution in step S11 is not particularly limited as long as the metal component precursors are uniformly mixed. For example, the precursors of the various metal components in step S11 are dissolved in water and sufficiently stirred.
According to the present invention, preferably, the rare earth metal component precursor, the non-noble metal component precursor selected from one or more of group VB, VIII, IB, IIB, the non-noble metal component precursor of group VIIB, and the noble metal component precursor may each be independently selected from water-soluble salts of each metal component, such as nitrates, chlorides, chlorates, sulfates, etc., preferably nitrates and/or chlorides. Further preferably, the precursor of manganese is potassium permanganate and/or manganese chloride.
In the present invention, the kind and amount of the coprecipitate are not particularly limited as long as the coprecipitation reaction can be smoothly performed. The coprecipitate is one selected conventionally in the art, and preferably, the coprecipitate is a carbonate, more preferably one or a mixture of ammonium carbonate, potassium carbonate and sodium carbonate, and more preferably ammonium carbonate.
In step S12, the coprecipitate may be introduced in the form of a solution to perform a coprecipitation reaction with the first solution. The concentrations of the first solution and the solution of the coprecipitate are not particularly limited in the present invention, as long as the dissolution concentration is less than the solubility at the time of preparation, thereby ensuring that the coprecipitation reaction can sufficiently occur.
Preferably, the coprecipitation reaction is carried out at a pH of 8 to 10, preferably 8.5 to 9.5. The pH of the coprecipitation reaction can be adjusted by adding an acid and/or a base, and the kind of the acid and/or the base is not particularly limited, and examples thereof include aqueous ammonia.
According to the invention, the method also comprises the step of carrying out solid-liquid separation on a reaction product obtained by the coprecipitation reaction to obtain a solid product. In the present invention, the solid-liquid separation method is not particularly limited as long as the reaction product can be subjected to solid-liquid separation. For example, the solid-liquid separation may be filtration or centrifugation.
Preferably, the drying conditions of step S13 include: the temperature is 60-300 ℃ and the time is 0.5-6h.
Preferably, the firing conditions of step S13 include: the temperature is 300-800 ℃ and the time is 1-8h.
The noble metal component of the present invention may be introduced in step S2, step S3, partially in step S2 and partially in step S3, preferably by introducing in step S3, this preferred embodiment being more favorable for the dispersion of the noble metal.
In the present invention, the precursor of the inorganic oxide matrix is any substance that can be converted into the oxide matrix by subsequent baking, and a person skilled in the art can appropriately select a specific kind of the inorganic oxide matrix, which is not described herein again. For example, the precursor of alumina may be selected from various sols or gels of aluminum, or aluminum hydroxide. The aluminium hydroxide may be selected from one or more of gibbsite, surge dawsonite, nordstrandite, diaspore, boehmite and pseudo-boehmite. Most preferably, the precursor of alumina is pseudo-boehmite.
According to the preparation method provided by the invention, the inorganic oxide matrix is alumina, preferably, before pulping, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix is/are required to be subjected to acidification treatment, the acidification treatment can be carried out by adopting a conventional technical means in the field, and further preferably, the acid used in the acidification treatment is hydrochloric acid.
The invention has wide selection range of the acidification treatment conditions, and preferably, the acidification treatment conditions comprise: the acid-aluminum ratio is (0.12-0.22): 1, the time is 20-40min.
In the present invention, the aluminum-acid ratio refers to a mass ratio of hydrochloric acid calculated as 36% by weight of concentrated hydrochloric acid to a precursor of alumina on a dry basis, unless otherwise specified.
Specific embodiments of the acidification peptization treatment can be as follows: and placing the alumina precursor in water, pulping and dispersing.
According to the present invention, there is no particular limitation on the method of mixing and beating the active metal precursor with the inorganic oxide substrate and/or the precursor of the inorganic oxide substrate and optionally the precursor of the noble metal component, and there is no particular limitation on the order of addition of the active metal precursor with the inorganic oxide substrate and/or the precursor of the inorganic oxide substrate and optionally the precursor of the noble metal component as long as the active metal precursor is brought into contact with the inorganic oxide substrate and/or the precursor of the inorganic oxide substrate and optionally the precursor of the noble metal component and water. When the pulping process also contains a precious metal component precursor, the specific mixing and pulping process can comprise: adding a noble metal component precursor (which can be introduced in a solution form) into the acidified inorganic oxide matrix, mixing and pulping, adding an active metal precursor, and drying and roasting the pulp to obtain a catalyst finished product.
According to the invention, the slurry in step S2 preferably has a solids content of 5 to 40% by weight.
The drying method in step S2 is preferably spray drying, and in the present invention, spray drying may be performed according to a conventional technique in the art, and the present invention is not particularly limited thereto. Those skilled in the art can select suitable spray drying conditions according to the average particle size of the target catalyst, and preferably spray drying conditions are such that the spray-dried particles have an average particle size of 60 to 80 μm and a particle size distribution range of mainly 20 to 100 μm.
Preferably, the firing conditions of step S2 include: the temperature is 300-800 ℃ and the time is 1-5h.
The impregnation in step S3 according to the preparation method of the present invention may be performed according to conventional techniques in the art, and the present invention is not particularly limited thereto. For example, the impregnation method may be a saturated impregnation method, or an excess impregnation method, preferably an excess impregnation method.
According to the present invention, preferably, in step S3, the noble metal component precursor is hydrolyzed in an acid solution to prepare an impregnation liquid. Specifically, it is also possible to perform dilution (water may be added) or concentration (evaporation may be performed) after the hydrolysis, and then perform impregnation to provide the desulfurization denitration catalyst of a specific noble metal component loading.
Preferably, the acid is a water-soluble inorganic acid and/or organic acid, preferably one or a mixture of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
According to the invention, the acid is preferably used in such an amount that the pH of the impregnation solution is less than 6.0, preferably less than 5.0. The advantages of using this preferred embodiment are better uniformity of the dispersion of the active components and improved abrasion resistance of the finished catalyst.
The invention can obtain a solid product by filtering the mixture obtained after impregnation. Filtration may be carried out according to conventional techniques in the art.
In step S3 of the present invention, not only the solid product may be dried, but also only the solid product may be calcined, and the solid product may be dried and then calcined. The conditions for drying and calcining in the present invention are not particularly limited, and may be carried out according to the conventional techniques in the art. For example, the conditions of drying may include: the temperature is 60-150 ℃ and the time is 2-10h. The conditions of the baking in step S3 are not particularly limited, and the baking may be performed in air or an inert atmosphere (e.g., nitrogen), and the baking conditions in step S3 are preferably: the temperature is 300-800 deg.C, and the time is 0.1-5h.
The desulfurization and denitrification catalyst provided by the invention is suitable for any SO-containing catalyst x And NO x The treatment of flue gas. Based on the above, the third aspect of the invention provides a desulfurization and denitrification catalyst for simultaneously removing SO from flue gas x And NO x Application in reactions. The desulfurization and denitrification catalyst provided by the invention is particularly suitable for removing SO in catalytic cracking regenerated flue gas x And NO x Preferably, the flue gas is catalytic cracking regeneration flue gas.
Preferably, the desulfurization and denitrification catalyst is mixed with SO x And NO x Contacting the flue gas;
preferably, SO is removed x And NO x The conditions of (a) are as follows: the temperature is 500-800 ℃, the pressure is 0.02-4MPa, and the volume space velocity of the flue gas is 100-50000h -1 (ii) a Further preferably, the temperature is 550-780 ℃, the pressure is 0.03-2MPa, and the volume space velocity of the flue gas is 200-20000h -1 . In the present invention, there is no special featureIn a very limited case, the pressure is a gauge pressure.
The invention is used for treating SO in flue gas x And NO x The content of (B) is selected from a wide range as long as SO is contained x And NO x I.e., to facilitate removal of both. Preferably, SO is contained in the flue gas x In an amount of 0.001-0.5 vol%, NO x The content of (B) is 0.001-0.03 vol%; further preferably, in the flue gas, SO x The content of (A) is 0.002-0.2 vol%, NO x The content of (B) is 0.002-0.2 vol%.
Preferably, SO is contained in the flue gas x With NO x The volume content ratio of (A) is 1-1.4, preferably 1-1.2. This preferred embodiment is more advantageous in increasing the removal efficiency of both.
Preferably, the flue gas is catalytic cracking regeneration flue gas. The catalytic cracking regeneration flue gas contains SO x And NO x In addition, it may contain CO, CO 2 、H 2 And (4) O component.
In the present invention, the ppm refers to a volume concentration unless otherwise specified.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
The following examples and comparative examples all use commercially available materials, the specific manufacturers and grades are shown in table 1 below:
TABLE 1 manufacturer and model of raw materials used in examples and comparative examples
Example 1
S1, preparing an active metal precursor: 360mL of deionized water was weighed into a beaker, and La was added with stirring 2 O 3 30g of lanthanum nitrate in terms of Co 2 O 3 Cobalt nitrate 3.5g by mass and2.5g of manganese chloride, expressed as MnO mass, until complete dissolution. 54g of ammonium carbonate is weighed and dissolved in 215mL of deionized water, the mixture is stirred to be fully dissolved, the mixed solution of metal nitrate is added into the ammonium carbonate solution under the stirring state, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture after complete precipitation, leaching the mixture with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting the mixture for 6 hours at 700 ℃ in air atmosphere, and grinding the mixture to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing with Al 2 O 3 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum stone, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.
S3, preparation of a catalyst: weighing a palladium precursor and dilute hydrochloric acid 1:1, dissolving mutually, adding deionized water for dilution, preparing a palladium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of palladium chloride solution with the concentration of 5.6g/L according to the mass of palladium of 0.0045 g. And (2) dipping the semi-finished product of the catalyst by using a palladium-containing solution as a dipping solution to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-1.
Example 2
S1, preparing an active metal precursor: 150mL of deionized water was weighed into a beaker, and La was added with stirring 2 O 3 Lanthanum nitrate, in terms of Co, 10g by mass 2 O 3 1.6g of cobalt nitrate by mass and 3.4g of manganese chloride by mass of MnO until complete dissolution. Weighing 22.5g of ammonium carbonate, dissolving in 90mL of deionized water, stirring until the ammonium carbonate is fully dissolved, adding the metal nitrate mixed solution into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. Pumping the mixture with complete precipitationFiltering, leaching with deionized water, drying the filter cake mixture obtained by filtering at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing Al 2 O 3 To 40g of aluminum oxide in terms of mass, 330mL of water and 6g of 36 wt% concentrated hydrochloric acid were added and the mixture was pulped. And (3) weighing 10g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 20 percent.
S3, preparation of a catalyst: weighing a palladium precursor and dilute hydrochloric acid 1:1, dissolving mutually, adding deionized water for dilution, preparing a palladium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of palladium chloride solution with the concentration of 5.6g/L according to the mass of palladium of 0.0030 g. And (2) dipping the semi-finished product of the catalyst by using a palladium-containing solution as a dipping solution to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-2.
Example 3
S1, preparing an active metal precursor: 360mL of deionized water was weighed into a beaker, and La was added with stirring 2 O 3 30g of lanthanum nitrate in terms of Co 2 O 3 2.6g of cobalt nitrate by mass and 3.4g of manganese chloride by mass of MnO until complete dissolution. 54g of ammonium carbonate is weighed and dissolved in 215mL of deionized water, the mixture is stirred to be fully dissolved, the mixed solution of metal nitrate is added into the ammonium carbonate solution under the stirring state, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture after complete precipitation, leaching the mixture with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting the mixture for 6 hours at 700 ℃ in air atmosphere, and grinding the mixture to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing Al 2 O 3 Aluminum having a mass of 40g380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to the stone, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.
S3, preparation of a catalyst: weighing a palladium precursor and dilute hydrochloric acid 1:1, dissolving mutually, adding deionized water for dilution, preparing a palladium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of palladium chloride solution with the concentration of 5.6g/L according to the mass of palladium of 0.0030 g. And (2) soaking the semi-finished catalyst by using a palladium-containing solution as a soaking solution to obtain a solid product, drying the solid product at 120 ℃, and roasting for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-3.
Example 4
According to the method of the embodiment 1, except that the consumption of the aluminum oxide is reduced, the mass percentage of the non-noble metal active component in the semi-finished product of the microsphere catalyst is adjusted to 50%.
Specifically, S1, preparation of an active metal precursor: 360mL of deionized water was weighed into a beaker, and La was added with stirring 2 O 3 30g of lanthanum nitrate in terms of Co 2 O 3 3.5g cobalt nitrate by mass and 2.5g manganese chloride by mass of MnO until complete dissolution. 54g of ammonium carbonate is weighed and dissolved in 215mL of deionized water, the mixture is stirred to be fully dissolved, the mixed solution of metal nitrate is added into the ammonium carbonate solution under the stirring state, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture after complete precipitation, leaching the mixture with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting the mixture for 6 hours at 700 ℃ in air atmosphere, and grinding the mixture to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing Al 2 O 3 To 20g of aluminum oxide in terms of mass, 240mL of water and 3g of 36 wt% concentrated hydrochloric acid were added and the mixture was pulped. Weighing 20g ofAdding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a semi-finished product of the catalyst microsphere. The non-noble metal active component accounts for 50 percent of the mass of the prepared microsphere catalyst semi-finished product.
S3, preparation of a catalyst: weighing a palladium precursor and dilute hydrochloric acid 1:1, dissolving mutually, diluting with deionized water to prepare a palladium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of palladium chloride solution with the concentration of 5.6g/L according to the mass of palladium of 0.0060 g. And (2) soaking the semi-finished catalyst by using a palladium-containing solution as a soaking solution to obtain a solid product, drying the solid product at 120 ℃, and roasting for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-4.
Example 5
S1, preparing an active metal precursor: 340mL of deionized water was weighed into a beaker, and La was added with stirring 2 O 3 30g of lanthanum nitrate in terms of Co 2 O 3 1g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. 51g of ammonium carbonate is weighed and dissolved in 205mL of deionized water, the mixture is stirred until the ammonium carbonate is fully dissolved, the mixed solution of the metal nitrate is added into the ammonium carbonate solution under the stirring state, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing Al 2 O 3 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.
S3, preparation of a catalyst: weighing a palladium precursor and dilute hydrochloric acid 1:1, dissolving mutually, adding deionized water for dilution, preparing a palladium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of palladium chloride solution with the concentration of 5.6g/L according to the mass of palladium of 0.0030 g. And (2) dipping the semi-finished product of the catalyst by using a palladium-containing solution as a dipping solution to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-5.
Example 6
S1, preparing an active metal precursor: 330mL of deionized water was weighed into a beaker, and La was added with stirring 2 O 3 15g of lanthanum nitrate in terms of mass, in terms of Co 2 O 3 15g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. Weighing 49.5g of ammonium carbonate, dissolving the ammonium carbonate in 200mL of deionized water, stirring the solution until the ammonium carbonate is fully dissolved, adding the mixed solution of the metal nitrate into the ammonium carbonate solution under the stirring state, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying the filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing Al 2 O 3 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.
S3, preparation of a catalyst: weighing a palladium precursor and dilute hydrochloric acid 1:1, dissolving mutually, adding deionized water for dilution, preparing a palladium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of palladium chloride solution with the concentration of 5.6g/L according to the mass of palladium of 0.0045 g. And (2) dipping the semi-finished product of the catalyst by using a palladium-containing solution as a dipping solution to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-6.
Example 7
S1, preparing an active metal precursor: 365mL of deionized water is weighed in a beaker, and La is added with stirring 2 O 3 30g of lanthanum nitrate in terms of Co 2 O 3 3.5g of cobalt nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. 54.75g of ammonium carbonate is weighed and dissolved in 220mL of deionized water, the mixture is stirred to be fully dissolved, the mixed solution of metal nitrate is added into the ammonium carbonate solution under the stirring state, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) performing suction filtration on the mixture with complete precipitation, leaching with deionized water, drying a filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing Al 2 O 3 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting for 4 hours at 700 ℃ in the air atmosphere to obtain a semi-finished product of the catalyst microsphere. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.
S3, preparation of a catalyst: weighing a precursor of ruthenium and diluted hydrochloric acid 1:1, dissolving mutually, diluting with deionized water to prepare a ruthenium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of ruthenium chloride solution with the concentration of 5.6g/L according to the mass of ruthenium of 0.0045 g. And (3) impregnating the ruthenium-containing solution serving as an impregnation liquid into the semi-finished catalyst to obtain a solid product, drying the solid product at 120 ℃, and roasting the solid product at 700 ℃ in an air atmosphere for 4 hours to obtain the catalyst S-7.
Example 8
S1, preparing an active metal precursor: 365mL of deionized water is weighed in a beaker, and CeO is added under stirring 2 30g of cerium nitrate in terms of Fe 2 O 3 3.5g of ferric nitrate by mass and 3g of manganese chloride by mass of MnO until complete dissolution. 54.75g of ammonium carbonate is weighed and dissolved in 220mL of deionized water, the mixture is stirred to be fully dissolved, the mixed solution of metal nitrate is added into the ammonium carbonate solution under the stirring state, and a certain amount of ammonia water is added to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the mixture with complete precipitation, leaching with deionized water, drying the filter cake mixture obtained by suction filtration at 120 ℃, roasting at 700 ℃ in air atmosphere for 6 hours, and grinding to obtain the active metal precursor.
S2, preparing a catalyst semi-finished product: weighing Al 2 O 3 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And (3) weighing 20g of active metal precursor, adding the active metal precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 200 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain a catalyst microsphere semi-finished product. The mass percentage of the non-noble metal active component in the semi-finished product of the prepared microspherical catalyst is 33 percent.
S3, preparation of a catalyst: weighing a palladium precursor and dilute hydrochloric acid 1:1, dissolving mutually, adding deionized water for dilution, preparing a palladium chloride solution with the concentration of 5.6g/L, weighing 15g of catalyst microsphere semi-finished product with the pH of 2, and weighing a certain amount of palladium chloride solution with the concentration of 5.6g/L according to the mass of palladium of 0.0045 g. And (2) dipping the semi-finished product of the catalyst by using a palladium-containing solution as a dipping solution to obtain a solid product, drying the solid product at 120 ℃, and roasting the dried solid product for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst S-8.
Comparative example 1
Weighing La 2 O 3 Dissolving 30g of lanthanum nitrate in a beaker, weighing 45g of ammonium carbonate to be completely dissolved in the beaker, adding the lanthanum nitrate solution into the ammonium carbonate solution under stirring under the stirring condition, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. Subjecting the mixture obtained above toAnd (4) performing suction filtration, namely drying the filter cake mixture obtained by suction filtration at 120 ℃, roasting for 6 hours at 700 ℃ in air atmosphere, and grinding to obtain a catalytic precursor L.
Weighing with Co 2 O 3 Completely dissolving 5g of cobalt nitrate by mass in a beaker, weighing 7.5g of ammonium carbonate, completely dissolving in the beaker, adding the cobalt nitrate solution into the ammonium carbonate solution under stirring under the condition of stirring, and adding a certain amount of ammonia water to maintain the pH value of the solution at 9. And (3) carrying out suction filtration on the obtained mixture, drying the filter cake mixture obtained by suction filtration at 120 ℃, roasting for 6 hours at 700 ℃ in air atmosphere, and grinding to obtain the active metal precursor C.
And fully and mechanically mixing the active metal precursor L and the active metal precursor C obtained in the previous two steps to obtain a mixed precursor.
Weighing Al 2 O 3 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. And (3) adding 20g of mixed precursor into the acidified inorganic oxide matrix, mixing and stirring, drying the slurry at 120 ℃, and roasting at 700 ℃ in air atmosphere for 4 hours to obtain the catalyst D-1.
Comparative example 2
The catalyst was prepared as follows: weighing 15g of OX50 (SiO) 2 ) The powder and the palladium-containing mass 0.0045g a certain amount of the palladium chloride solution prepared in example 1 was weighed out. The palladium chloride solution was added dropwise to the OX50 powder and mixed well by constant stirring. And placing the obtained mixture in an oven at 120 ℃ until the mixture is dried, and then roasting the mixture for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst D-2.
Comparative example 3
30g of La were weighed 2 O3 and 5g of Co 2 O 3 And fully and mechanically mixing to obtain a mixed precursor.
Weighing Al 2 O 3 380mL of water and 6g of 36 wt% concentrated hydrochloric acid were added to 40g of aluminum oxide in terms of mass, and the mixture was pulped. Adding 20g of mixed precursor into the acidified inorganic oxide matrix, mixing and stirring the mixtureDrying the slurry at 120 ℃, and roasting the slurry for 4 hours at 700 ℃ in an air atmosphere to obtain the catalyst D-3.
Comparative example 4
Comparative catalyst D-4 was prepared according to the procedure described in CN 110787834A. Weighing alumina, kaolin, magnesium, boron, lanthanum, platinum, titanium, alumina sol and ethyl acetate according to the proportion in the table 1, mixing, adding 5 times of water, soaking at 85 ℃ for more than 3 hours, and stirring at 85 ℃ for 3 hours after soaking to uniformly disperse the alumina, the kaolin, the magnesium, the boron, the lanthanum, the platinum, the titanium, the alumina sol and the ethyl acetate. Spray drying the slurry at the temperature of 300 ℃, and screening to obtain particles less than or equal to 200 mu m; and roasting the obtained particles at the temperature of 500 ℃ for 4 hours, fully grinding the obtained active metal precursor, tabletting, and sieving to obtain the final flue gas desulfurization and denitrification catalyst, which is recorded as D-4.
Table 2 mass percent of each raw material in comparative example 4
Performance testing
The component content determination: the contents of the components of the desulfurization and denitrification catalysts obtained in examples 1 to 8 were measured by X-ray fluorescence spectroscopy (XRF), and specifically, they were compiled by petrochemical analysis (RIPP test method), yang Cui, and published by scientific publishing company in 1990. Specific results are shown in the following table.
Table 3 examples 1 to 8 contents (wt%) of respective components of desulfurization and denitrification catalyst
(II) activity evaluation: the evaluation criterion of the catalyst activity in the invention is SO in the reaction product x And NO x Change in concentration as a measure of SO in the product x And NO x The content is measured by an FT-IR Fourier infrared flue gas analyzer, and a fixed bed micro-reaction experimental device is adopted for evaluation. The evaluation results of the activity of the desulfurization and denitrification catalyst are expressed in terms of conversion.
Conversion calculation method:
wherein, C (inlet) Refers to the inlet SO of the experimental device x Or NO x The concentration of (c); c (outlet) Refers to the outlet SO of the experimental device x Or NO x The concentration of (c).
For simultaneously reducing NO and SO in flue gas by using the desulfurization and denitrification catalyst provided by the above examples and comparative examples 2 The effect of the emissions was evaluated. The catalytic cracking reaction-regeneration evaluation is carried out on a small-sized fixed bed simulated flue gas device, the loading amount of a catalyst is 1.5g, the reaction temperature is 680 ℃, the pressure is 0.03MPa, the volume flow (standard condition) of raw material gas is 1500mL/min, and the volume space velocity is about 15000 h -1 . The feed gas contained 1200ppm of NO and 1200ppm of SO 2 The balance being N 2 . Analyzing the gas product by an on-line infrared analyzer to obtain reacted SO 2 And NO concentration. The results of the evaluation time of 0.5h are shown in Table 4, and the results of the evaluation time of 1.5h are shown in Table 5.
TABLE 40.5 comparison of desulfurization and denitrification performances of different desulfurization and denitrification catalysts
Note: NO alone and SO alone in Table 4 2 Respectively mean that the feed gas contains only 1200ppm NO or 1200ppm SO 2 。
As can be seen from Table 4, the present invention was completed within the first 0.5hProvided for simultaneously reducing SO in flue gas x With NO x Compared with the catalyst phase prepared by the prior art under the same evaluation conditions, the desulfurization and denitrification catalyst prepared by the method is mixed with NO and SO 2 The pollutant removal rate in the reaction is obviously superior to that of the single SO feeding 2 Gas and NO gas alone. The desulfurization and denitrification catalyst provided by the invention has higher catalytic conversion activity, and particularly the catalytic conversion activity of NO is greatly improved in the combined catalytic process.
TABLE 51.5 comparison of desulfurization and denitrification performances of different desulfurization and denitrification catalysts
| 1.5h Total conversion (%) | combination-NO | combination-SO 2 | NO alone | Single SO 2 |
| S-1 | 55 | 33 | <2 | 27 |
| S-2 | 39 | 19 | <2 | 15 |
| S-3 | 44 | 29 | <2 | 25 |
| S-4 | 61 | 39 | <2 | 33 |
| S-5 | 32 | 30 | <2 | 29 |
| S-6 | 26 | 25 | <2 | 24 |
| S-7 | 51 | 31 | <2 | 25 |
| S-8 | 48 | 32 | <2 | 27 |
| D-1 | <2 | 24 | <2 | 23 |
| D-2 | 8 | <2 | 8 | <2 |
| D-3 | 4 | 7 | <2 | 6 |
| D-4 | 3 | 15 | 4 | 18 |
Note: NO alone and SO alone in Table 5 2 Respectively means that the feed gas contains only 1200ppm NO or 1200ppm SO 2 。
As can be seen from Table 5, the SO reduction provided by the present invention is within 1.5h x With NO x Although the total conversion rate of the catalyst for desulfurization and denitrification of pollutants is reduced, compared with the catalyst phase prepared by the prior art under the same evaluation conditions, NO and SO are mixed in 2 The removal rate of pollutants in the reaction is still obviously superior to that of the single SO 2 Gas and NO gas alone.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A desulfurization and denitrification catalyst is characterized by comprising the following components in percentage by weight based on the total weight of the catalyst,
calculated by oxide: 25-92wt% of inorganic oxide matrix, 6-70wt% of rare earth metal component, 1-12wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-10wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.01-1.5wt% of noble metal component.
2. The desulfurization and denitrification catalyst according to claim 1, comprising, in terms of weight percent based on the total weight of the catalyst,
calculated by oxide: 40-85wt% of inorganic oxide matrix, 12-60wt% of rare earth metal component, 2-10wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-8wt% of non-noble metal component selected from VIIB group;
calculated by elements: noble metal component 0.02-1.2wt%;
preferably, the catalyst comprises, in weight percent based on the total weight of the catalyst,
calculated by oxide: 45-80wt% of inorganic oxide matrix, 12-48wt% of rare earth metal component, 2-8wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 2-5wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.02-1.0wt% of noble metal component.
3. The SOx/NOx catalyst of claim 1, wherein the rare earth metal component is selected from one or a mixture of lanthanum, cerium, praseodymium and neodymium, and more preferably lanthanum;
the non-noble metal component of one or more of VB, VIII, IB and IIB groups is selected from one or more of mixture of iron, cobalt, nickel, copper, zinc and vanadium, and cobalt is more preferable;
the non-noble metal component in the VIIB group is manganese;
the noble metal component is selected from one or a mixture of more of ruthenium, rhodium, rhenium, platinum, palladium, silver, iridium and gold, more preferably one or a mixture of more of platinum, palladium and rhodium, and most preferably palladium;
the inorganic oxide matrix is selected from one or a mixture of more of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite, and is preferably alumina.
4. The desulfurization and denitrification catalyst according to any one of claims 1 to 3, wherein the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB is (0.6-18): 1, more preferably (2-12): 1, more preferably (3-6): 1.
5. A preparation method of a desulfurization and denitrification catalyst comprises the following steps:
s1, preparing an active metal precursor: adopting a coprecipitation method or a sol-gel method;
s2, preparing a catalyst semi-finished product: mixing and pulping an active metal precursor, an inorganic oxide matrix and/or a precursor of the inorganic oxide matrix and optionally a precursor of a noble metal component to obtain a slurry, and drying and roasting the slurry;
the method also optionally includes: s3, taking a solution containing a precursor of a noble metal component as an impregnation solution, impregnating the semi-finished product of the catalyst obtained in the step S2 to obtain a solid product, and drying and roasting the solid product;
wherein, the active metal in the active metal precursor comprises rare earth metal components, one or more non-noble metal components selected from VB, VIII, IB and IIB groups and VIIB group non-noble metal components;
the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the precursor of the noble metal component are used in such amounts that the prepared catalyst comprises the following components in percentage by weight based on the total weight of the catalyst: 25-92wt% of inorganic oxide matrix, 6-70wt% of rare earth metal component, 1-12wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-10wt% of non-noble metal component selected from VIIB group; calculated by elements: 0.01-1.5wt% of noble metal component.
6. The production method according to claim 5, wherein the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix, and the precursor of the noble metal component are used in amounts such that the catalyst is produced including, in terms of weight percentage, based on the total weight of the catalyst,
calculated by oxide: 40-85wt% of inorganic oxide matrix, 12-60wt% of rare earth metal component, 2-10wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 1-8wt% of non-noble metal component selected from VIIB group;
calculated by elements: noble metal component 0.02-1.2wt%;
preferably, the active metal precursor, the inorganic oxide matrix and/or the precursor of the inorganic oxide matrix and the precursor of the noble metal component are used in such amounts that the catalyst is produced comprising, in percent by weight, based on the total weight of the catalyst,
calculated by oxide: 45-80wt% of inorganic oxide matrix, 12-48wt% of rare earth metal component, 2-8wt% of non-noble metal component selected from one or more of VB, VIII, IB and IIB group, and 2-5wt% of non-noble metal component selected from VIIB group;
calculated by elements: 0.02-1.0wt% of noble metal component;
preferably, the molar ratio of the rare earth metal component to the non-noble metal component selected from one or more of groups VB, VIII, IB and IIB in the active component precursor is (0.6-18): 1, more preferably (2-12): 1, and even more preferably (3-6): 1.
7. The production method according to claim 5 or 6, wherein the rare earth metal component is selected from one or a mixture of lanthanum, cerium, praseodymium and neodymium, more preferably lanthanum;
the non-noble metal component of one or more of VB, VIII, IB and IIB groups is selected from one or more of mixture of iron, cobalt, nickel, copper, zinc and vanadium, and cobalt is more preferable;
the non-noble metal component in the VIIB group is manganese;
the noble metal component is selected from one or more of ruthenium, rhodium, rhenium, platinum, palladium, silver, iridium and gold, more preferably is one or more of platinum, palladium and rhodium, and most preferably is palladium;
the inorganic oxide matrix is selected from one or a mixture of more of alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite, and is preferably alumina.
8. The production method according to any one of claims 5 to 7, wherein an active metal precursor is obtained in step S1 by a coprecipitation method;
preferably, the co-precipitation method comprises:
s11, preparing a first solution containing a rare earth metal component precursor, one or more non-noble metal component precursors selected from VB, VIII, IB and IIB groups and a VIIB non-noble metal component precursor;
s12, carrying out coprecipitation reaction on the first solution and a coprecipitator;
and S13, drying and roasting a solid product obtained by the coprecipitation reaction.
9. The production method according to claim 8, wherein the rare earth metal component precursor, the non-noble metal component precursor selected from one or more of groups VB, VIII, IB, IIB, the group VIIB non-noble metal component precursor, and the noble metal component precursor are each independently selected from nitrates and/or chlorides of the respective metal components;
preferably, the coprecipitator is carbonate, preferably one or a mixture of ammonium carbonate, potassium carbonate and sodium carbonate;
preferably, the coprecipitation reaction is carried out at a pH of 8 to 10;
preferably, the conditions for the firing in step S13 are: the temperature is 300-800 ℃ and the time is 1-8h.
10. The production method according to any one of claims 5 to 9, wherein the slurry in step S2 has a solid content of 5 to 40wt%;
preferably, the conditions for the calcination in step S2 are: the temperature is 300-800 ℃ and the time is 1-5h.
11. The production method according to any one of claims 5 to 10, wherein in step S3, a noble metal component precursor is hydrolyzed in an acid solution to obtain a desired impregnation solution;
preferably, the acid solution is a water-soluble inorganic acid and/or organic acid, preferably a mixture of one or more of hydrochloric acid, nitric acid, phosphoric acid and acetic acid;
preferably, the acid is used in an amount such that the pH of the impregnation solution is less than 6.0, preferably less than 5.0;
preferably, the baking conditions in step S3 are: the temperature is 300-800 deg.C, and the time is 0.1-5h.
12. The desulfurization and denitrification catalyst according to any one of claims 1 to 4 or the desulfurization and denitrification catalyst prepared by the preparation method according to any one of claims 5 to 11, wherein SO is removed from flue gas simultaneously x And NO x Application in reactions.
13. The use of the desulfurization/denitrification catalyst according to claim 12, wherein the desulfurization/denitrification catalyst is mixed with SO x And NO x Contacting the flue gas;
wherein SO is removed x And NO x The conditions of (a) are as follows: the temperature is 500-800 ℃, the pressure is 0.02-4MPa, and the volume space velocity of the flue gas is 100-50000h -1 ；
Preferably, in flue gasSO x In an amount of 0.001-0.5 vol%, NO x The content of (B) is 0.001-0.3 vol%;
preferably, the flue gas is catalytic cracking regeneration flue gas.
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| CA3232113A CA3232113A1 (en) | 2021-09-09 | 2022-09-09 | Catalyst for reducing sox and nox in flue gas, preparation method therefor, and method for removing sox and nox from flue gas |
| KR1020247011967A KR20240055104A (en) | 2021-09-09 | 2022-09-09 | Catalyst for reducing SOx and NOx in smoke, method for producing the same, and method for removing SOx and NOx from smoke |
| PCT/CN2022/118245 WO2023036317A1 (en) | 2021-09-09 | 2022-09-09 | Catalyst for reducing sox and nox in flue gas, preparation method therefor, and method for removing sox and nox from flue gas |
| TW111134309A TW202319117A (en) | 2021-09-09 | 2022-09-12 | Catalyst for reducing sox and NOx in flue gas, preparation method therefor, and method for removing sox and NOx from flue gas |
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