CN113244949B - High-durability BEA molecular sieve catalyst with core-shell structure, preparation method and application thereof - Google Patents
High-durability BEA molecular sieve catalyst with core-shell structure, preparation method and application thereof Download PDFInfo
- Publication number
- CN113244949B CN113244949B CN202110716496.2A CN202110716496A CN113244949B CN 113244949 B CN113244949 B CN 113244949B CN 202110716496 A CN202110716496 A CN 202110716496A CN 113244949 B CN113244949 B CN 113244949B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sieve catalyst
- bea
- core
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 78
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011258 core-shell material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052772 Samarium Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims 2
- 229910052789 astatine Inorganic materials 0.000 claims 1
- 239000004312 hexamethylene tetramine Substances 0.000 claims 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229960004011 methenamine Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 208000005374 Poisoning Diseases 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 231100000572 poisoning Toxicity 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 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 4
- 239000000463 material Substances 0.000 description 4
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-O cyclohexylammonium Chemical compound [NH3+]C1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-O 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention provides a high-durability BEA molecular sieve catalyst with a core-shell structure, a preparation method and application thereof. The catalyst provided by the invention has excellent ammonia adsorption capacity, low-temperature activity, temperature operation window and N in Urea-SCR technology by virtue of the intrinsic activity of Sm element2Selectivity and structural stability, and the use of a high stability oxide shell to protect the core BEA molecular sieve catalyst from large amounts of SO2And high-temperature water vapor, on the other hand, the active components are inhibited from migrating at high temperature, and the durability is further improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a high-durability BEA molecular sieve catalyst with a core-shell structure, a preparation method and application thereof.
Background
The motor vehicle output and sales volume of China is steadily at the top of the world for 11 years continuously, the motor vehicle keeping volume of 2020 breaks through 3.72 hundred million vehicles, and the problem of the emission of mobile source pollutants such as motor vehicles and the like is increasingly highlighted. According to annual report of environmental management of China Mobile resources (2020), the total emission of four pollutants of motor vehicles in the whole country in 2019 is preliminarily accounted to 1603.8 ten thousand tons. Wherein carbon monoxide (CO), Hydrocarbon (HC), and Nitrogen Oxide (NO)X) The emission amount of Particulate Matters (PM) is 771.6 ten thousand tons, 189.2 ten thousand tons, 635.6 ten thousand tons and 7.4 ten thousand tons respectively, which is one of the main sources of urban air pollution in China. NO, one of the main pollutants of motor vehicle exhaustXIs an excellent source for causing severe environmental problems such as haze, photochemical smog, acid rain and the like, and seriously harms the health of people.
As internationally recognized catalytic clean-up diesel NOXThe selective catalytic reduction (scr) technology is a main technical route for diesel engines to achieve national VI emission regulations, and the technology has been applied in various countries. The catalyst is the core and key of the SCR technology. The temperature range of the tail gas of the diesel vehicle under the normal working condition is wider (200 plus 500 ℃), and the temperature is generally lower than 200 ℃ during cold start, so that higher requirements are provided for the low-temperature activity of the catalyst. Meanwhile, instantaneous high temperature generated during DPF active regeneration reaches more than 750 ℃, and the catalyst is required to have better hydrothermal stability. In addition, the exhaust gas atmosphere of diesel vehicles contains a large amount of hydrocarbon, which provides a challenge to the hydrocarbon poisoning resistance of the catalyst. In the IV/V stage of China, a vanadium-based catalyst (V) taking titanium-tungsten powder as a carrier2O5-WO3/TiO2) The catalyst has wide application in China, but has high toxicity and low temperatureLow conversion rate, poor high-temperature selectivity and the like. Molecular sieve catalysts are of great interest because of their high activity, good selectivity, environmental friendliness, and the like. After transition metal exchanged ZSM-5 molecular sieve catalysts have been reported to have better SCR activity since the 90 s of the last century, copper-based molecular sieve catalysts such as FAU, CHA, BEA, LTA, etc. were successively investigated for the removal of NOx by SCR technology. The iron-based BEA structure molecular sieve has good low-temperature performance and nitrogen selectivity, and the catalytic material belongs to a green environment-friendly material. However, the actual exhaust gas atmosphere in practical applications is usually accompanied by a high temperature, high hydrothermal and sulfur-containing atmosphere, resulting in a material that is susceptible to deactivation.
The patent with publication number CN112536066A relates to a preparation method of a mesoporous Fe-Beta molecular sieve catalyst containing a core-shell structure, which constructs a Fe-C-Al precursor with the core-shell structure, and the prepared Fe-Beta molecular sieve catalyst has a mesoporous structure communicated with the core-shell structure, and has the advantages of high product crystallinity, high specific surface area, rich mesopores and uniform iron distribution. But SO2Molecules can enter the core through the mesopores, contact with the Fe/BETA catalyst and deactivate the catalyst, and the catalyst does not have the capability of resisting sulfur poisoning.
The patent with the publication number of CN107029782A relates to a core-shell catalyst for FCC regenerated flue gas denitration and a preparation method thereof, and the method has complicated steps including equal-volume impregnation and ultrasonic dispersion, and has long preparation period and can not be realized in the actual large-scale production process.
The patent with the publication number of CN105253895A relates to a Beta molecular sieve with high content of Fe in a framework and a preparation method thereof, and the method fixes Fe in the framework structure of the molecular sieve, thereby greatly improving the thermal stability, but being incapable of solving the problem of sulfur poisoning resistance.
Disclosure of Invention
In view of the above, the present invention aims to provide a BEA molecular sieve catalyst with a high durable core-shell structure, a preparation method and applications thereof, SO as to improve the SO resistance of the catalyst2Poisoning ability and high temperature hydrothermal resistance.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the high-durability BEA molecular sieve catalyst with the core-shell structure comprises an inner core and a shell layer wrapped on the inner core, wherein the inner core is a modified Sm-based BEA molecular sieve catalyst, and the shell layer is made of an oxide.
Preferably, the material of the shell layer is at least one of alumina, cerium oxide, titanium oxide, silicon oxide and zirconium oxide.
Preferably, the thickness of the shell layer is less than or equal to 20 nm.
A preparation method of a BEA molecular sieve catalyst with a high-durability core-shell structure comprises the following steps:
(1) preparing a modified Sm-based BEA molecular sieve catalyst;
(2) mixing the modified Sm-based BEA molecular sieve catalyst with an oxide to prepare a BEA molecular sieve catalyst precursor with a core-shell structure;
(3) centrifuging a precursor of the core-shell structure BEA molecular sieve catalyst to obtain a solid, and drying and roasting the solid to prepare the core-shell structure BEA molecular sieve catalyst; preferably, the roasting temperature is 400-600 ℃, and the roasting time is 2-5 h.
Preferably, the specific operation of step (1) comprises the following steps:
ion exchange, dissolving a soluble active component samarium precursor in deionized water, stirring until the soluble active component samarium precursor is completely dissolved, adding a BEA structure molecular sieve, adding an accelerant, heating and stirring to perform an ion exchange reaction, preparing an Sm/BEA molecular sieve catalyst precursor, adding a soluble auxiliary agent, heating and stirring to prepare a modified Sm/BEA molecular sieve catalyst precursor;
reducing the temperature of the modified Sm/BEA molecular sieve catalyst precursor to below 50 ℃, and starting negative pressure to evaporate the solvent to obtain powder;
soaking for multiple times, adding deionized water and soluble auxiliary agent into the powder, stirring for dissolving for soaking, reacting for 10-60 min, evaporating under reduced pressure again to obtain powder, and repeating for 2-3 times;
and (3) fine grinding, namely fine grinding the powder obtained after multiple soakings, drying and roasting to obtain the modified Sm-based BEA molecular sieve catalyst with the particle size of 100 nm.
Preferably, the soluble active component samarium precursor is samarium salt which is soluble in water and has a molecular weight of less than 1000, the BEA structure molecular sieve comprises at least one of Beta and CIT-6, the promoter comprises at least one of acetic acid, phosphoric acid, formic acid, nitric acid, carbonic acid, ammonium carbonate, ammonium nitrate, ammonium phosphate and ammonium acetate, the soluble auxiliary agent is a compound which is soluble in water and has a molecular weight of less than 1000 and contains metal elements, and the metal elements comprise at least one of Fe, Cu, Ce, Mn, Y, Pr, Ni, Co, Pt, Pd and Rh; preferably, the soluble active component samarium precursor is at least one of samarium nitrate and samarium chloride, the BEA structure molecular sieve is a Beta molecular sieve, and the metal elements are Fe, Cu, Ce and Mn.
Preferably, the reaction temperature of ion exchange is 60-140 ℃, the reaction time of ion exchange is 1-10h, the water content in the powder obtained by reduced pressure evaporation is less than 6.5 wt%, the molar ratio of the soluble active component samarium precursor to the soluble auxiliary agent is 1:0.01-10, the ratio of the mass sum of the soluble active component samarium precursor and the soluble auxiliary agent to the mass of the BEA structure molecular sieve is 0.001-0.2: 1, the mass ratio of the singly supplemented deionized water to the BEA structure molecular sieve is 0.5-10:1, finely grinding for 1-6h, drying at 80-100 ℃ after finely grinding for 6-24 h; preferably, the reaction temperature of ion exchange is 60-80 ℃, the reaction time of ion exchange is 4-8h, the molar ratio of the soluble active component samarium precursor to the soluble auxiliary agent is 1:0.1-3, the ratio of the mass sum of the soluble active component samarium precursor and the soluble auxiliary agent to the mass of the BEA structure molecular sieve is 0.02-0.05: 1, the mass ratio of the singly supplemented deionized water to the BEA structure molecular sieve is 1-2.5: 1, the time for fine grinding is 3-4 h.
Preferably, the specific operation of step (2) comprises the following steps:
performing ultrasonic dispersion, namely placing the modified Sm-based BEA molecular sieve catalyst in an organic alcohol solvent for ultrasonic dispersion to obtain a suspension;
performing electrostatic adsorption, namely adding ammonia water into the suspension to adjust the pH to 8-10, forming electrostatic adsorption charges on the surfaces of the modified Sm-based BEA molecular sieve catalyst powder particles, adding a shell oxide precursor, and stirring and dispersing to form a uniform mixed solution;
and (3) coating a shell layer, namely heating the mixed solution for reflux reaction, and coating the shell layer to obtain the BEA molecular sieve catalyst precursor with the core-shell structure.
Preferably, the organic alcohol solvent comprises at least one of ethanol, methanol, ethylene glycol, glycerol and isopropanol, and the modified Sm-based BEA molecular sieve catalyst comprises the following components in percentage by weight: the organic alcohol solvent has a mass concentration of 0.0001-10g/ml, and the shell oxide precursor comprises tetrabutyl titanate, titanium sol, aluminum sol, silica sol, water glass, tetraethyl silicate, titanic acid, and ZrO2、TiO2、Al2O3、SiO2、CeO2Cerium nitrate, sodium aluminate, sodium silicate, aluminum nitrate, cerous cyclohexylammonium, shell oxide precursor: the mass concentration of the organic alcohol solvent is 0.001-30g/ml, the temperature of the reflux reaction is 25-50 ℃, and the reflux reaction time is 8-24 h; preferably, the organic alcohol solvent is methanol or ethanol, and the modified Sm-based BEA molecular sieve catalyst is as follows: the mass concentration of the organic alcohol solvent is 0.005-2g/ml, and the mass concentration of the shell oxide precursor is as follows: the mass concentration of the organic alcohol solvent is 0.1-10 g/ml.
The application of the BEA molecular sieve catalyst with the high-durability core-shell structure in selective reduction elimination of nitrogen oxides in tail gas.
Compared with the prior art, the high-durability BEA molecular sieve catalyst with the core-shell structure, the preparation method and the application thereof have the following advantages:
(1) the high-durability BEA molecular sieve catalyst with the core-shell structure shows excellent ammonia adsorption capacity, low-temperature activity, temperature operation window and N in the Urea-SCR technology by virtue of the intrinsic activity of Sm element2Selectivity and structural stability;
(2) the preparation method of the high-durability BEA molecular sieve catalyst with the core-shell structure adopts multiple soakings, can obviously improve the enrichment condition of oxides on the surface of the molecular sieve carrier, and ensures the low-temperature performance and the temperature window of the molecular sieve SCR catalyst;
(3) the high-durability core-shell structure BEA molecular sieve catalyst utilizes a high-stability oxide shell layer to protect the core BEA molecular sieve catalyst from contacting a large amount of SO2High temperature water vapor, the other partyThe surface inhibition active component is migrated at high temperature, so that the durability is improved, meanwhile, the modified Sm/BEA catalyst serving as the kernel has high activity and high thermal stability, and the kernel and the shell are mutually cooperated;
(4) the shell layer and the inner core of the high-durability BEA molecular sieve catalyst with the core-shell structure can form a unique core-shell interface, the core-shell interface effect can provide a stable catalytic oxidation reduction circulation place, and meanwhile, the shell layer has strong HC poisoning resistance, so that the catalyst has a wide reaction temperature window and strong HC poisoning resistance;
(5) the preparation method of the high-durability BEA molecular sieve catalyst with the core-shell structure is continuous and easy to operate, the thickness of the prepared nano shell layer is uniform, the consistency of products with the core-shell structure is good, and the preparation method is suitable for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows Fe-Sm/Beta @ TiO in accordance with an embodiment of the present invention2Scanning electron micrographs of the sample and its EDS;
FIG. 2 shows Fe-Sm/Beta @ TiO in an embodiment of the present invention2X-ray diffraction patterns of three samples of Fe-Sm/Beta and H-Beta;
FIG. 3 shows 2.5Fe-0.5Sm/Beta @ TiO in accordance with an embodiment of the present invention2、2.5Fe-0.5Sm/Beta@TiO2-Δ、0.5Fe-2.5Sm/Beta@TiO2，0.5Cu-2.5Sm/Beta@TiO2、2.5Fe-0.5Sm/Beta@TiO2NO of-. DELTA.XAnd (4) a schematic diagram of removal efficiency.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
In the examples of the invention and comparative examples, NH3Simulated smoke composition used for SCR performance testing: 500 ppm NO, 500 ppm NH3，5% O2，N2For balancing gas, the total flow is 1000 ml/min, and the reaction space velocity is 30000 h-1。
In the examples of the invention and comparative examples, the low temperature Performance index T50When NO is representedXThe temperature corresponding to the conversion rate of 50%; temperature window index T90When NO is representedXThe temperature range corresponding to a conversion of more than 90%. N is a radical of2Selectivity is the arithmetic mean of the nitrogen selectivity data at each test temperature point within the range of 175-525 ℃.
The present invention will be described in detail with reference to the following embodiments and drawings, it being understood that the preferred embodiments described herein are merely for the purpose of illustrating and explaining the present invention and are not intended to limit the present invention.
Unless otherwise indicated, all numbers expressing quantities such as temperature, time, and mass percent of slurry feed, as used in the specification and claims are to be understood as being modified in all instances by the term "about" and not necessarily by the term "about".
1. Preparation of Sm/Beta catalyst
Weighing 10g of samarium nitrate, stirring and dissolving the samarium nitrate in 250g of deionized water, adding a 5g H type Beta molecular sieve, adding acetic acid to adjust the pH to be about =3, heating to 80 ℃ to perform ion exchange reaction for 6 hours, performing high-speed centrifugation to realize solid-liquid separation, repeatedly washing the solid with 50ml of deionized water for 3 times until the filtrate is colorless, drying at 120 ℃ for 8 hours, testing the content of Sm element by ICP (inductively coupled plasma) and marking as a 2.5Sm/Beta catalyst.
Similarly, the sample with the mass fraction of 0.1-7.5% can be prepared by adjusting the adding amount of the samarium nitrate, and the sample is marked as 0.1-7.5 Sm/Beta catalyst.
2. Preparation of modified Sm/Beta catalyst
Selecting 10g of 0.5Sm/Beta catalyst powder, uniformly stirring and dispersing the powder in 300 ml of deionized water, adding 1.08 g of ferric nitrate into the solution according to the stoichiometric ratio (molar ratio) of Fe/Sm =5:1, stirring and dissolving, carrying out ion exchange reaction at the constant temperature of 80 ℃ for 6 hours, starting reduced pressure evaporation, evaporating on an optional evaporator until the water content in the dry powder is 6%, and stopping evaporation; supplementing 15 g of deionized water into the dry powder, fully mixing and wetting, then carrying out reduced pressure evaporation again, repeating the steps for 3 times, drying the obtained powder, testing the Fe element content by XRF (X-ray diffraction) for 2.5 wt%, finely grinding in a planetary ball mill for 2h, intensively distributing the particle size of laser particle size analysis particles to about 100nm, stopping grinding, filtering, washing and drying, and roasting at 550 ℃ for 5h under the protection of nitrogen to obtain catalyst powder which is marked as a 2.5Fe-0.5Sm/Beta catalyst.
In the same way, catalyst powders with different Sm contents are selected, and series (0.5-3.5) Fe- (0.1-3.5) Sm/Beta catalysts are prepared by adjusting the addition of ferric nitrate according to the stoichiometric ratio.
Similarly, different additive elements are selected, and the addition amounts of manganese nitrate, cerium nitrate, cobalt nitrate and copper nitrate are respectively adjusted according to the stoichiometric ratio to prepare series (0.5-3.5) Mn- (0.1-3.5) Sm/Beta, (0.5-3.5) Co- (0.1-3.5) Sm/Beta, (0.5-3.5) Ce- (0.1-3.5) Sm/Beta and (0.5-3.5) Cu (0.1-3.5) Sm/Beta catalysts.
Example 1
Weighing 0.15 g of 2.5Fe-0.5Sm/Beta sample as a core catalyst, ultrasonically dispersing in 150ml of absolute ethyl alcohol for 3 hours, adding 1g of PVP, and continuing to perform ultrasonic treatment for 1 hour until the PVP is completely dissolved. Adding 0.5ml ammonia water, stirring for 1 hr, adjusting pH =9, dripping 1ml tetrabutyl titanate, condensing and refluxing at 45 deg.C for 12 hr, centrifuging, washing, vacuum drying at 60 deg.C for 12 hr, and calcining at 500 deg.C under nitrogen atmosphere for 3 hr, wherein the mark is 2.5Fe-0.5Sm/Beta @ TiO2A core-shell catalyst.
Example 2
The conditions and flow of the catalyst preparation in this example were the same as in example 1 except that the amount of aqueous ammonia was 0.4ml and the amount of tetrabutyl titanate was 1.75 ml. The prepared core-shell catalyst is marked as 2.5Fe-0.5Sm/Beta @ TiO2-Δ
Example 3
The preparation conditions and preparation flow of the catalyst of this example were the same as in example 1, except thatThe core catalyst is 0.5Fe-2.5Sm/Beta, and the high-durability core-shell catalyst is prepared and is marked as 0.5Fe-2.5Sm/Beta @ TiO2。
Example 4
The conditions and flow for the preparation of the catalyst of this example were the same as in example 1 except that the core catalyst was selected to be 0.5Cu to 2.5Sm/Beta, designated 0.5Cu to 2.5Sm/Beta @ TiO2。
Comparative example 1
Referring to the preparation conditions and preparation flow of the Sm/Beta catalyst preparation examples, a 2.5Sm/Beta catalyst was prepared. Different from the example 1, the additive doping modification and the shell coating are not carried out, and the mark is Sm/Beta.
Comparative example 2
Referring to the preparation conditions and the preparation flow in the preparation examples of the Sm/Beta catalyst and the modified Sm/Beta catalyst, 2.5Fe-1.5Sm/Beta catalyst is prepared. Unlike example 1, no shell coating was performed and was labeled 2.5Fe-0.5 Sm/Beta.
Comparative example 3
The catalyst of this example was prepared under the same conditions and in the same manner as in example 1 except that tetrabutyl titanate was used in an amount of 5 ml. The prepared core-shell catalyst is marked as 2.5Fe-0.5Sm/Beta @ TiO2-ΔΔ
Fresh sample performance verification
The core-shell catalysts of examples 1 to 4 and comparative examples 1 to 3 of the invention are prepared into 40-60 mesh powder samples, and NH is carried out on the powder samples in a miniature fixed bed reactor3-SCR catalytic performance evaluation. The size of the quartz reaction tube used is 15mm, and the evaluation test temperature rise rate is 5 ℃/min. Simulated atmosphere composition: 500 ppm NO, 500 ppm NH3，5% O2，N2For balancing gas, the total flow rate is 1,000 ml/min, and the reaction space velocity is 30,000 h-1。
The results of the performance tests on the fresh samples of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
Aging Performance verification
The core-shell catalysts of examples 1-4 and comparative examples 1-3 of the invention are prepared into 40-60 mesh powder samples, and the powder samples are prepared into high-temperature hydrothermal aging samples through high-temperature hydrothermal treatment in a tubular furnace, wherein the treatment conditions are as follows: 10 vol% of water vapor and air as balance gas, aging at 750 deg.C for 24h, total flow rate of 1000 ml/min, and space velocity of 20000 h-1。
Preparing the core-shell catalysts of the examples 1-4 and the comparative examples 1-3 into a 40-60 mesh powder sample, performing sulfur poisoning treatment in a tubular furnace to prepare a sulfur aged sample, wherein the treatment conditions are as follows: 10 vol% of water vapor and air as balance gas, aging at 750 ℃ for 24h, with the total flow of 1,000 ml/min and the space velocity of 20,000 h-1。
Respectively carrying out NH treatment on the high-temperature hydrothermal aging sample and the sulfur aging sample on a miniature fixed bed reactor3-SCR catalytic performance evaluation. The size of the quartz reaction tube used is 15mm, and the evaluation test temperature rise rate is 5 ℃/min. Simulated atmosphere composition: 500 ppm NO, 500 ppm NH3，5% O2，N2For balancing gas, the total flow rate is 1,000 ml/min, and the reaction space velocity is 30,000 h-1。
The results of the aged sample performance test of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2
Fe-Sm/Beta@TiO2The scanning electron microscope image and the EDS image of the sample are shown in figure 1, and the microstructure and element mapping of the core-shell structure BETA molecular sieve catalyst can be observed.
Fe-Sm/Beta@TiO2The X-ray diffraction patterns of the three samples Fe-Sm/Beta and H-Beta are shown in FIG. 2, and the crystal phase structures of the samples can be judged. As can be seen from the figure, the three samples showed the same crystal phase structure, and it was confirmed that the crystal phase structures of the molecular sieve catalyst and the BEA molecular sieve were not destroyed during the preparation of the core-shell structure, and a large amount of oxides were not generated.
Examples 1 to 4 and pairsSample to NO ratio 3XThe removal efficiency is shown in fig. 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The high-durability BEA molecular sieve catalyst with the core-shell structure is characterized in that: comprises a kernel and a shell layer wrapped on the kernel, wherein the kernel is a modified Sm-based BEA molecular sieve catalyst, the shell layer is made of oxide, and the shell layer is made of at least one of alumina, cerium oxide, titanium oxide, silicon oxide and zirconium oxide,
the preparation method of the high-durability BEA molecular sieve catalyst with the core-shell structure comprises the following steps:
(1) the preparation method of the modified Sm-based BEA molecular sieve catalyst comprises the following steps:
ion exchange, dissolving a soluble active component samarium precursor in deionized water, stirring until the soluble active component samarium precursor is completely dissolved, adding a BEA structure molecular sieve, adding an accelerant, heating and stirring to perform an ion exchange reaction to prepare the Sm/BEA molecular sieve catalyst precursor, adding a soluble auxiliary agent, heating and stirring to prepare the modified Sm/BEA molecular sieve catalyst precursor, wherein the soluble active component samarium precursor is samarium salt which is dissolved in water and has a molecular weight of less than 1000, the BEA structure molecular sieve comprises at least one of Beta and CIT-6, the accelerant comprises at least one of acetic acid, phosphoric acid, formic acid, nitric acid, carbonic acid, ammonium carbonate, ammonium nitrate, ammonium phosphate and ammonium acetate, the soluble auxiliary agent is a compound which is dissolved in water and has a molecular weight of less than 1000 and contains metal elements, and the metal elements comprise Fe, Cu, Ce, Mn, Y, Pr, Ni, Co, Pt, Pr, Fe, Pr, and Mn, At least one of Pd and Rh;
reducing the temperature of the modified Sm/BEA molecular sieve catalyst precursor to below 50 ℃, and starting negative pressure to evaporate the solvent to obtain powder;
soaking for multiple times, adding deionized water and soluble auxiliary agent into the powder, stirring for dissolving for soaking, reacting for 10-60 min, evaporating under reduced pressure again to obtain powder, and repeating for 2-3 times;
fine grinding, fine grinding the powder obtained after multiple soakings, drying and roasting to obtain the modified Sm-based BEA molecular sieve catalyst with the particle size of 100 nm;
(2) mixing the modified Sm-based BEA molecular sieve catalyst with a shell oxide precursor to prepare a BEA molecular sieve catalyst precursor with a core-shell structure, wherein the specific operation comprises the following steps:
performing ultrasonic dispersion, namely placing the modified Sm-based BEA molecular sieve catalyst in an organic alcohol solvent for ultrasonic dispersion to obtain a suspension;
performing electrostatic adsorption, namely adding ammonia water into the suspension to adjust the pH to 8-10, forming electrostatic adsorption charges on the surfaces of the modified Sm-based BEA molecular sieve catalyst powder particles, adding a shell oxide precursor, and stirring and dispersing to form a uniform mixed solution;
coating a shell layer, namely heating the mixed solution for reflux reaction, and coating the shell layer to obtain a BEA molecular sieve catalyst precursor with a core-shell structure;
(3) and centrifuging the precursor of the core-shell structure BEA molecular sieve catalyst to obtain a solid, and drying and roasting the solid to prepare the core-shell structure BEA molecular sieve catalyst.
2. The high-durability core-shell structure BEA molecular sieve catalyst according to claim 1, characterized in that: the thickness of the shell layer is less than or equal to 20 nm.
3. The high-durability core-shell structure BEA molecular sieve catalyst according to claim 1, characterized in that: the reaction temperature of ion exchange is 60-140 ℃, the reaction time of ion exchange is 1-10h, the water content in the powder obtained by reduced pressure evaporation is less than 6.5 wt%, the molar ratio of the soluble active component samarium precursor to the soluble auxiliary agent is 1:0.01-10, the mass ratio of the sum of the soluble active component samarium precursor and the soluble auxiliary agent to the BEA structure molecular sieve is 0.001-0.2: 1, the mass ratio of the deionized water to the BEA structure molecular sieve supplemented once is 0.5-10:1, the fine grinding time is 1-6h, the drying temperature after the fine grinding is 80-100 ℃, and the drying time is 6-24 h.
4. The high-durability core-shell structure BEA molecular sieve catalyst according to claim 1, characterized in that: the organic alcohol solvent comprises at least one of ethanol, methanol, glycol, glycerol and isopropanol, and the modified Sm-based BEA molecular sieve catalyst comprises the following components in percentage by weight: the mass concentration of the organic alcohol solvent is 0.0001-10g/mL, and the precursor of the shell oxide comprises tetrabutyl titanate, titanium sol, aluminum sol, silica sol, water glass, tetraethyl silicate, titanic acid and ZrO2、TiO2、Al2O3、SiO2、CeO2At least one of cerous nitrate, sodium aluminate, sodium silicate, aluminum nitrate and cerous hexamethylene tetramine, a precursor of the BEA molecular sieve catalyst with a core-shell structure: the mass concentration of the organic alcohol solvent is 0.001-30g/mL, the temperature of the reflux reaction is 25-50 ℃, and the reflux reaction time is 8-24 h.
5. Use of the high-durability core-shell structure BEA molecular sieve catalyst according to any one of claims 1 to 4 for selective reduction elimination of nitrogen oxides in exhaust gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110716496.2A CN113244949B (en) | 2021-06-28 | 2021-06-28 | High-durability BEA molecular sieve catalyst with core-shell structure, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110716496.2A CN113244949B (en) | 2021-06-28 | 2021-06-28 | High-durability BEA molecular sieve catalyst with core-shell structure, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113244949A CN113244949A (en) | 2021-08-13 |
| CN113244949B true CN113244949B (en) | 2021-10-12 |
Family
ID=77189785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110716496.2A Active CN113244949B (en) | 2021-06-28 | 2021-06-28 | High-durability BEA molecular sieve catalyst with core-shell structure, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113244949B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115364892B (en) * | 2022-08-05 | 2024-03-01 | 东风商用车有限公司 | Vanadium-based catalyst for diesel vehicle tail gas aftertreatment system and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029782A (en) * | 2016-10-09 | 2017-08-11 | 中国石油大学(北京) | It is a kind of for nucleocapsid catalyst of FCC regenerated flue gas denitrations and preparation method thereof |
| CN109701524A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Remove the catalyst and preparation method thereof of nitrogen oxides |
| CN111085259A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silicon oxide and SAPO-34 zeolite composite material and synthetic method thereof |
| CN111099623A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | AEI/MFI composite structure molecular sieve and synthetic method thereof |
-
2021
- 2021-06-28 CN CN202110716496.2A patent/CN113244949B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029782A (en) * | 2016-10-09 | 2017-08-11 | 中国石油大学(北京) | It is a kind of for nucleocapsid catalyst of FCC regenerated flue gas denitrations and preparation method thereof |
| CN109701524A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Remove the catalyst and preparation method thereof of nitrogen oxides |
| CN111085259A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silicon oxide and SAPO-34 zeolite composite material and synthetic method thereof |
| CN111099623A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | AEI/MFI composite structure molecular sieve and synthetic method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Rare-earth ion exchanged Cu-SSZ-13 zeolite from organo template-free synthesis with enhanced hydrothermal stability in NH3-SCR of NOx";Zheenchao Zhao等;《Catal.sci.technol.》;20181126;第9卷;第241-245页 * |
| "氧化物薄膜包覆的Fe基Beta分子筛核壳结构催化剂的设计、制备、表征及对NH3-SCR反应的研究";刘计省;《中国博士学位论文全文数据库 工程科技I辑》;20190115;B014-258 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113244949A (en) | 2021-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8673809B2 (en) | Low level noble metal-supporting three-way catalyst | |
| CN102861605B (en) | Diesel vehicle oxidation catalyst with low SO2 oxidation activity and preparation method of catalyst | |
| CN111545193B (en) | Hollow core-shell structure catalyst for catalytic oxidation of nitrogen oxide and preparation method thereof | |
| CN108067291B (en) | A kind of preparation method of honeycomb rare earth based denitration catalyst | |
| CN105314648B (en) | CHA type Si-Al molecular sieves and its preparation method and application | |
| CN103263912A (en) | Diesel vehicle tail gas purifying catalyst and preparation method thereof | |
| CN110180582A (en) | A kind of diesel vehicle oxidation catalyst and preparation method thereof | |
| CN111715302B (en) | Poisoning-resistant metal oxide denitration catalyst and preparation method thereof | |
| CN106732581A (en) | A kind of Ru/CeTiO for low-temperature SCR reactionXThe preparation method of catalyst | |
| CN105312083B (en) | CHA type sial phosphorus molecular sieve and its preparation method and application | |
| CN113559850B (en) | Manganese-based composite oxide catalyst and preparation method and application thereof | |
| WO2023216447A1 (en) | Cu-cha and h-aei composite catalyst, and preparation method therefor and application thereof | |
| CN106669685A (en) | Oxygen carrier, and preparation method and application thereof | |
| CN111686716B (en) | WOxLow-temperature SCR (selective catalytic reduction) flue gas denitration catalyst with modified carbon nano tube loaded with metal oxide, and preparation method and application thereof | |
| WO2023226668A1 (en) | High sulfur-resistant zirconium-based pillared clay supported catalyst and preparation method therefor and application thereof | |
| CN107233895B (en) | Oxidation catalyst for purifying motor vehicle tail gas and preparation method thereof | |
| CN110694670A (en) | Preparation method of molecular sieve for purifying diesel vehicle tail gas | |
| CN113649015A (en) | Flue gas denitration catalyst and preparation method and application thereof | |
| CN113244949B (en) | High-durability BEA molecular sieve catalyst with core-shell structure, preparation method and application thereof | |
| KR100416735B1 (en) | Catalyst for purifying exhaust gas from car and method for preparing thereof | |
| CN114345402A (en) | Preparation method of iron-based molecular sieve catalyst | |
| CN112221488A (en) | Novel core-shell structure catalyst for synergistic denitration and demercuration and preparation method thereof | |
| CN110639609A (en) | Core-shell structure Cu/SAPO-34@ meso-TiO2Catalytic material, preparation method and application thereof | |
| CN107597183B (en) | Preparation method of denitration catalyst | |
| CN115318303A (en) | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230223 Address after: Room 526, main building, No. 68, Xianfeng East Road, Dongli District, Tianjin Patentee after: CATARC AUTOMOTIVE TEST CENTER (TIANJIN) Co.,Ltd. Patentee after: CHINA AUTOMOTIVE TECHNOLOGY AND RESEARCH CENTER Co.,Ltd. Address before: 300457 TEDA MSD-B1-1907, 62 Second Avenue, Binhai New Area Development Zone, Tianjin Patentee before: CATARC (TIANJIN) AUTOMOTIVE ENGINEERING RESEARCH INSTITUTE Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20210813 Assignee: SHANGHAI GOTEK CATALYST Co.,Ltd. Assignor: CATARC AUTOMOTIVE TEST CENTER (TIANJIN) Co.,Ltd. Contract record no.: X2023980052975 Denomination of invention: High durability core-shell structure BEA molecular sieve catalyst, preparation method and application Granted publication date: 20211012 License type: Common License Record date: 20231218 |
|
| EE01 | Entry into force of recordation of patent licensing contract |