CN110102338A - A kind of ammoxidation catalyst and preparation method thereof of high nitrogen selective - Google Patents
A kind of ammoxidation catalyst and preparation method thereof of high nitrogen selective Download PDFInfo
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- CN110102338A CN110102338A CN201910358277.4A CN201910358277A CN110102338A CN 110102338 A CN110102338 A CN 110102338A CN 201910358277 A CN201910358277 A CN 201910358277A CN 110102338 A CN110102338 A CN 110102338A
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 111
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 53
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 49
- 241000269350 Anura Species 0.000 claims abstract description 47
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002808 molecular sieve Substances 0.000 claims abstract description 46
- -1 rare earth modified aluminium oxide Chemical class 0.000 claims abstract description 45
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 43
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 150000003624 transition metals Chemical class 0.000 claims abstract description 33
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 229910052878 cordierite Inorganic materials 0.000 claims description 6
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims 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 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 39
- 229910021529 ammonia Inorganic materials 0.000 abstract description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- GIGQFSYNIXPBCE-UHFFFAOYSA-N alumane;platinum Chemical compound [AlH3].[Pt] GIGQFSYNIXPBCE-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01D53/9436—Ammonia
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of ammoxidation catalysts and preparation method thereof of high nitrogen selective.The catalyst includes the coating coated on carrier and carrier.Coating is made of platinum, rare earth modified aluminium oxide, transition metal modified SAPO molecular sieve；Coating load amount is 120~200g/L；The load capacity of noble metal platinum is 0.1~10g/ft3；The weight ratio of rare earth modified aluminium oxide middle rare earth and aluminium oxide is 0~10:90~100, the weight ratio of rare earth modified aluminium oxide and transition metal modified SAPO molecular sieve is 10~90:10~90, and transition metal weight accounts for the 0.5~3.5% of transition metal modified molecular sieve in transition metal modified SAPO molecular sieve.The catalyst is prepared by rare earth modified aluminium oxide, noble metal platinum supported rare earth modified aluminas, transition metal modified SAPO molecular sieve, the preparation of slurry, coating coating and the method preparation present invention of catalyst drying, calcining, method is simple, it can be used for reducing the discharge of ammonia, and the nitrogen selective of ammoxidation catalyst is significantly improved, efficiently inhibit the generation of high temperature nitrogen oxides.
Description
Technical field
The invention belongs to catalyst technical field, be mainly concerned with a kind of high nitrogen selective ammoxidation catalyst and its
Preparation method,.
Background technique
Ammoxidation catalyst is a kind of by NH3It is oxidized to N2, efficiently realize NH3The technology of conversion, but ammonia was aoxidizing
NO, NO easily generated in journey2Equal by-products, increase NOxDischarge, lead to NOxDischarge it is not up to standard.NOxIt is acid rain, photochemistry cigarette
The main reason for environmental problems such as mist, ozone hole, and there is significant impact to human health.Therefore, ammonia oxygen is avoided
The key core problem for changing the secondary pollution that catalyst generates during the reaction is to improve NH3N in oxidation process2Selection
Property.
Traditional noble metal base ammoxidation catalyst is loaded using platinum on alumina, to NH3Processing capacity it is very strong, but
It is that such catalyst can generate a large amount of by-product N in reaction temperature section2O、NO、NO2, lead to N2Selectivity is poor, and to ring
Certain pollution is caused in border, and emission reduction effect is not achieved.
EP544282B1 discloses a kind of catalyst, by V/W/Ti catalyst and modenite or aluminium oxide or silica
The combination of carried noble metal platinum.The platinum of low concentration is supported on modenite, in ammonia and NOxReaction in, NO at 350 DEG CxTurn
Change efficiency is negative value, illustrates that ammonia is oxidized to NO by noble metalx；However individually there is V/W/Ti catalyst high ammonia to let out
Dew, the two is combined, and be can effectively reduce ammonia leakage and is improved N2 selectivity.But vanadium containing catalysts at 550 DEG C due to existing
The risk of vanadium volatilization, is limited by six regulation of diesel vehicle state in application process.
CN103476495B discloses a kind of ammoxidation catalyst and has used its waste gas purification apparatus and exhaust gas net
Change method, using the double-deck coated structure, overlying catalyst layer is by silica, tungsten oxide, ceria and zirconium dioxide shape
At composite oxides and zeolite composition；Lower catalyst oxidant layer is by one of titanium dioxide, silica, alchlor or several
Kind or zeolite-loaded noble metal and obtain.Although there is high NH in 230~400 DEG C of reactions3Transformation efficiency, but at 400 DEG C
New NO is generated with the oxidation of ammoniax, lead to N2Selectivity reduces, and is unfavorable for NOxEmission reduction.
The coating of above-mentioned ammoxidation catalyst includes two kinds of components.A kind of component is oxidized form, has oxygen for ammonia
The property changed (passing through the oxidation of noble metal), another component is V/W/Ti reduced form, has reproducibility for nitrogen oxides.Pass through oxygen
The ammonia of leakage is converted N by the property changed coating2、NO、NO2, NO that reproducibility coating generates ammoxidationxIt is reduced to N2, by double
The synergistic effect of coating oxidation and reproducibility improves the N of monolithic catalyst2Selectivity.
But the catalyst of the above-mentioned type is in high temperature or generating portion NOx, N2Selectivity be unable to satisfy present state
Six diesel vehicle regulations are to NOxRequirement.Therefore, it develops high ammoxidation performance and efficiently inhibits high temperature NO, NO2、N2What O was generated
Ammoxidation catalyst becomes current necessity and target.
Summary of the invention
Present invention solves the technical problem that essentially consist in improve ammoxidation catalyst high temperature aoxidize ammonia when generate NO,
NO2Equal by-products problem, provides a kind of ammoxidation catalyst and preparation method thereof of high nitrogen selective.
In order to achieve the above object, The technical solution adopted by the invention is as follows:
A kind of ammoxidation catalyst of high nitrogen selective, including the coating coated on carrier and carrier, it is characterised in that:
The coating is made of platinum, rare earth modified aluminium oxide, transition metal modified SAPO molecular sieve；The coating load amount be 120~
200g/L；The load capacity of the noble metal platinum is 0.1~10g/ft3；The rare earth modified aluminium oxide middle rare earth and oxygen
The weight ratio for changing aluminium is 0~10:90~100, the weight of the rare earth modified aluminium oxide and transition metal modified SAPO molecular sieve
Than for 10~90:10~90.
Further, the rare earth oxide in the rare earth modified aluminium oxide includes lanthana, cerium oxide, praseodymium oxide, oxygen
Change one or more of neodymium, yttrium oxide.
Further, the SAPO molecular sieve (SAPO-n, n=18,34,44), SAPO molecular sieve is by SiO2、Al2O3、P2O5
Composition, SiO2With Al2O3Molar ratio be 0.1~100.
Further, the transition metal includes one or more of copper and iron.
Further, the carrier is through type carrier, and carrier medium is cordierite.
A kind of preparation method of the ammoxidation catalyst of high nitrogen selective, which comprises the following steps:
1, the preparation of rare earth modified aluminium oxide
The rare earth metal salt solutions of 0.01~0.1g/mL are added in aluminium oxide, are sufficiently stirred, dries, then calcines,
Obtain rare earth modified aluminium oxide.
2, noble metal platinum supported rare earth modified aluminas
It is 0.1~10g/ft according to the load capacity of noble metal platinum3, noble metal platinum solution needed for calculating.By rare earth modified oxygen
Change aluminium, noble metal platinum solution are add to deionized water, and are sufficiently stirred, and are adjusted solution ph to 4~6.5, are obtained noble metal platinum
The rare earth modified alumina solution of load.
3, the preparation of transition metal modified SAPO molecular sieve
The preparation method of transition metal modified SAPO is the transition of blank SAPO molecular sieve and 0.005mol/L~5mol/L
Metal salt solution is prepared by one or more of hydrothermal crystallizing, ion exchange, infusion process, then by drying, calcining, is obtained
To transition metal modified molecular sieve；It is calculated with metallic element, transition metal weight accounts for transition metal modified SAPO molecular sieve weight
The 0.5~3.5% of amount.
4, the preparation of slurry
The modified oxidized aluminum solutions of noble metal platinum supported rare earth, transition metal modified SAPO molecular sieve, binder are added to
In deionized water, the modified oxidized aluminum solutions of noble metal platinum supported rare earth, transition metal modified SAPO molecular sieve and binder it is total
The weight ratio of quality and deionized water is 1:0.8~1.4, is sufficiently stirred, and forms slurry, is then ground, will slurry when grinding
Expect that partial size D90 control range is 1~25 μm.
5, coating coating and catalyst drying, calcining
Slurry prepared by step 4 is coated on monolithic substrate with 120-200g/L load capacity, is then dried, forges
It burns to get ammoxidation catalyst of the invention；Wherein catalyst coating load amount after calcining is 120~200g/L；
Further, drying temperature is 120~200 DEG C in step 1, drying time 6~for 24 hours；Maturing temperature is 550~600
DEG C, 3~4h of calcination time.
Further, added noble metal platinum solution is platinum nitrate, chloroplatinic acid, one in four ammino platinum of acetic acid in step 2
Kind is several.
Further, blank SAPO molecular sieve is Na in step 3+Type, H+Type, NH4 +One or more of type；In step 3
Added transition metal salt solution is transition metal copper salt solution and transition metal iron salt solutions, and transition metal copper salt solution is
One or more of copper nitrate, copper sulphate, copper acetate, copper chloride, stannous chloride；Transition metal iron salt solutions be ferric nitrate,
One or more of ferric sulfate, iron chloride, frerrous chloride, ferrous sulfide.
Drying temperature is 120~200 DEG C in the step 3, drying time 6~for 24 hours；Maturing temperature is 500~650 DEG C,
Calcination time is 3-4h.
Further, the binder that step 4 is added is Al2O3、SiO2、TiO2、ZrO2It is one or more of in powder or colloid；
The binder of addition is calculated by oxide, additive amount be rare earth modified aluminium oxide and cupric molecular sieve powder quality 1~
15%.
Further, coating uses upper feed technique or lower feed technique in step 5；Drying temperature is 120~200 DEG C, is done
Dry time 6~for 24 hours；Maturing temperature is 500~650 DEG C, and calcination time is 3~4h.
In a kind of ammoxidation catalyst of high nitrogen selective of the present invention, noble metal platinum supported rare earth modified aluminas is expensive
Metal platinum direct oxidation ammonia is N2Or NO or NO2；Transition metal modified SAPO molecular sieve absorption ammonia and NOx, carry out SCR also
Original reaction, can be effectively suppressed NO and NO2Generation.Catalyst of the invention not only improves low temperature active, but also can be improved high temperature N2
Selectivity, efficiently reduce NOxPollution.
The preparation method includes the preparation of rare earth modified aluminium oxide, noble metal platinum supported rare earth modified aluminas, transition gold
Belong to the modified preparation of SAPO molecular sieve, the preparation of slurry, grinding slurry, catalyst coating, catalyst drying, calcining.It is obtained
Catalyst has excellent NH3Transformation efficiency, high N2Selectivity；
The beneficial effects of the present invention are:
1, the ammoxidation catalyst of a kind of high nitrogen selective of the present invention, including the painting coated on carrier and carrier
Layer.Noble metal platinum supported rare earth modified aluminas, platinum can direct oxidation ammonia be N2Or NO or NO2；Transition metal modified SAPO points
Son sieve absorption ammonia and NOx, oxidation and SCR reaction are carried out, NO and NO can be effectively suppressed2Generation.
2, a kind of preparation method of the ammoxidation catalyst of high nitrogen selective of the present invention is simple and easy operation control.
Downstream of the catalyst being prepared for SCR catalyst uses, and can efficiently reduce the leakage of ammonia and can be significant in high temperature
Improve N2Selectivity.
Detailed description of the invention
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is Pt/Ce-Al-Cu-SAPO catalyst (A), Pt/Al-Cu-SAPO catalyst (B) and Pt/ Al2O3Catalyst
(C)NH3The relational graph of transformation efficiency and reaction temperature.
Fig. 2 is Pt/Ce-Al-Cu-SAPO catalyst (A), Pt/Al-Cu-SAPO catalyst (B) and Pt/ Al2O3Catalyst
(C)NOxThe relational graph of transformation efficiency and reaction temperature.
Fig. 3 is Pt/Ce-Al-Cu-SAPO catalyst (A), Pt/Al-Cu-SAPO catalyst (B) and Pt/ Al2O3Catalyst
(C)N2The relational graph of selectivity and reaction temperature.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below comes Case-based Reasoning and comparative example
Illustrate the present invention.All catalyst sizes are 1 inch and 2 inches of length of diameter below, and carrier is cylindrical cordierite ceramics.
Embodiment 1
A kind of ammoxidation catalyst of high nitrogen selective, including the coating coated on carrier and carrier, it is characterised in that:
The coating is made of platinum, rare earth modified aluminium oxide, transition metal modified SAPO molecular sieve；The coating load amount is 180g/
L；The load capacity of the noble metal platinum is 2g/ft3；The weight ratio of rare earth modified the aluminium oxide middle rare earth and aluminium oxide
For 10:90, the weight ratio of the rare earth modified aluminium oxide and transition metal modified SAPO molecular sieve is 10:90.
Rare earth oxide in the rare earth modified aluminium oxide is cerium oxide.
Further, the SAPO molecular sieve (SAPO-34), SAPO molecular sieve is by SiO2、Al2O3、 P2O5Composition, SiO2With
Al2O3Molar ratio be 0.5.
Further, the transition metal is copper.
A kind of preparation method of the ammoxidation catalyst of high nitrogen selective, which comprises the following steps:
1, the preparation of rare earth modified aluminium oxide
The cerous nitrate solution 25ml of 0.1g/mL is added in 10g aluminium oxide, 1h is stirred, places into baking oven and dry,
120 DEG C of drying 6h, are then placed in Muffle furnace, in 550 DEG C of calcining 3h, obtain cerium modified aluminas；The cerium modified oxygen of rare earth
Changing the mass ratio of cerium oxide and aluminium oxide in aluminium compound is 10:90.
2, noble metal platinum supported rare earth modified aluminas
It takes the modified oxidized aluminium powder 10g of cerium to be added in deionized water 20g, is sufficiently stirred, according to noble metal platinum
Load capacity is 2g/ft3, 0.21g platinum acid chloride solution is taken, is added drop-wise in cerium modified aluminium oxide, 2h is stirred, pH value is adjusted to 6, obtains
The rare earth modified alumina solution loaded to noble metal platinum.
3, the preparation of the modified SAPO molecular sieve of copper
Take the copper-bath 475mL and H of 0.1mol/L+It the SAPO molecular sieve powder 98g of type and is added in reaction kettle,
Using ion-exchange, 8h is reacted at a temperature of 80 DEG C, suction filtration is washed with deionized, until filtrate is colourless, then 140 DEG C of drying
6h obtains the modified SAPO molecular sieve of copper, copper content 2.1% in 550 DEG C of calcining 3h.
4, the preparation of slurry
It is 10:90 according to the weight ratio of rare earth modified aluminium oxide and transition metal modified SAPO molecular sieve, takes your gold platinum negative
Carry the modified SAPO molecular sieve 89.78g of rare earth modified alumina solution 30.15g, copper, binder Si glue 26.5g be added to from
140g in sub- water, the gross mass of the modified oxidized aluminum solutions of noble metal platinum supported rare earth, the SAPO molecular sieve of copper exchange and binder
Weight ratio with deionized water is 1:0.96, stirs 1h, forms slurry, and slurry partial size D90 is 10.5 μm.
5, coating coating and catalyst drying, calcining
Slurry prepared by step 4 is pressed into 180g/L load capacity, using upper coating method, is coated on cordierite carrier,
Then 160 DEG C of drying are carried out, 3h is roasted in 550 DEG C of air, obtains Pt/Ce-Al-Cu-SAPO integral catalyzer, are compiled
Number be A.
Embodiment 2
A kind of ammoxidation catalyst of high nitrogen selective, including the coating coated on carrier and carrier, it is characterised in that:
The coating is made of platinum, rare earth modified aluminium oxide, transition metal modified SAPO molecular sieve；The coating load amount is 180g/
L；The load capacity of the noble metal platinum is 2g/ft3；The weight ratio of rare earth modified the aluminium oxide middle rare earth and aluminium oxide
For 0:100, the weight ratio of the rare earth modified aluminium oxide and transition metal modified SAPO molecular sieve is 10:90.
Further, the SAPO molecular sieve (SAPO-34), SAPO molecular sieve is by SiO2、Al2O3、 P2O5Composition, SiO2With
Al2O3Molar ratio be 0.5.
Further, the transition metal is copper.
A kind of preparation method of the ammoxidation catalyst of high nitrogen selective, which comprises the following steps:
1, noble metal platinum Supported alumina
It takes alumina powder 11g to be added in deionized water 20g, is sufficiently stirred, the load capacity according to noble metal platinum is 2g/
ft3, 0.21g platinum acid chloride solution is taken, is added drop-wise in aluminium oxide, 2h is stirred, pH value is adjusted to 6, obtains the load oxidation of noble metal platinum
Aluminum solutions；
2, the preparation of copper modified molecular screen
Take the copper-bath 475mL and H of 0.1mol/L+It the SAPO molecular sieve powder 98g of type and is added in reaction kettle,
Using ion-exchange, 8h is reacted at a temperature of 80 DEG C, suction filtration is washed with deionized, until filtrate is colourless, then 140 DEG C of drying
6h obtains the modified SAPO molecular sieve of copper, copper content 2.1% in 550 DEG C of calcining 3h；
3, the preparation of slurry
Take noble metal platinum Supported alumina solution 30.21g, copper modified SAPO molecular sieve 89.78g, binder silica gel 26.5g
It is add to deionized water 150g, the gross mass of noble metal platinum Supported alumina solution, copper modified SAPO molecular sieve and binder
Weight ratio with deionized water is 1:0.96, stirs 1h, forms slurry；Slurry is ground；The slurry partial size D90 is 11
μm；
4, catalyst coats
Slurry described in step 3 is quantitatively coated on monolithic substrate；It is carried by 180g/L load capacity coated in cordierite
On body；
5, catalyst is dry, calcines
Catalyst is dry, calcines: catalyst described in step 5 is subjected to 160 DEG C of drying, roasts 3h in 550 DEG C of air,
Obtain Pt/Al-Cu-SAPO integral catalyzer, number B.
Comparative example 1
Load capacity according to noble metal platinum is 2g/ft3, 0.21g platinum acid chloride solution is taken, is added drop-wise in 101.8 g of aluminium oxide,
1h is stirred, binder silica gel 26.3g is then added, stirs 30min, adjusts pH to 6, obtains the oxidation aluminium paste of noble metal platinum load
Material；Above-mentioned slurry is ground, partial size D90 is 5 μm, is coated on cordierite carrier by 180g/L load capacity, 140 DEG C of drying, 550
DEG C roasting 3h, be made monoblock type Pt/Al2O3Catalyst is labeled as C.
It is as follows that embodiment 1, embodiment 2 and comparative example 1 test monolithic catalyst sample condition:
Catalyst specification is φ 25.4mm × 50.8mm, coating load amount 180g/L, the composition of reaction mixture gas are as follows:
[NH3]=750ppm [NO]=500ppm, [O2]=10%, [H2O]=7%, [CO2]=8%, N2Balance Air, air speed 100,
000h-1, 200 DEG C~500 DEG C of reaction temperature.NO,NO2、NH3And N2O gas is measured using infrared-gas pond.
Prepared integral catalyzer is carried out to active investigation, Fig. 1 A, B and C catalysis on fixed bed reactors
Agent is to NH3Transformation efficiency figure.As seen from Figure 1, the catalyst that prepared by the embodiment of the present invention 1 is specific noble-metal-supported
The catalyst coat that cerium modified aluminium oxide and the modified SAPO molecular sieve of copper are used as, compares embodiment 1, and addition rare earth cerium oxide has
Conducive to increase high temperature section catalyst to the conversion capability of ammonia.Compared to conventional precious metal catalyst C, preparation side provided by the invention
Catalyst A obtained by method is in 250-500 DEG C of section to NH3Conversion ratio reaches 90% or more, realizes conversion completely, A and B catalyst
Low temperature active be much higher than C catalyst.
Fig. 2 is A, B and C catalyst to NOxTransformation efficiency figure.As seen from Figure 2, prepared by the embodiment of the present invention 1
Catalyst is to NOxTransformation efficiency with higher, at 200 DEG C -500 DEG C, NOxTransformation efficiency is all larger than 90%.The high nitrogen of the present invention
Selective ammonia oxidation catalyst is in addition to NH3Oxidisability also have to NOxReproducibility, improve catalyst to NH3And NOx
Conversion.In comparative example 1, NOxTransformation efficiency be negative value, and increased with temperature, NOxConcentration increases.
Fig. 3 is A, B and C catalyst to N2Selective figure.As seen from Figure 3, catalysis prepared by the embodiment of the present invention 1
Agent is the catalyst coat that the cerium modified aluminium oxide of specific noble-metal-supported and SAPO molecular sieve are used as, in 200-500 DEG C of section
To N2Selectivity reaches 90% or more, hence it is evident that is better than conventional precious metal catalyst C.Since noble metal catalyst is to NH3Oxidation
Reaction mainly generates NOx, lead to NOxTransformation efficiency reduces and N2Selectivity reduces.Addition rare earth cerium oxide can effectively reduce height
Temperature section NOxDischarge.
By Fig. 1-3 it is found that the ammoxidation catalyst of high nitrogen selective of the present invention have urged than conventional precious metal
The higher ammonia transformation efficiency of agent, significantly improves NOxTransformation efficiency and N2Selectivity, therefore, one kind of the present invention
The ammoxidation catalyst of high nitrogen selective is widely portable to the ammonia decontamination of diesel motor exhaust leakage.
The Applicant declares that the present invention illustrates method detailed of the invention through the foregoing embodiment, but the present invention not office
It is limited to above-mentioned specific method, this means that the present invention, which necessarily relies on above-mentioned specific method, to be implemented.Technical field
Technical staff carries out equivalence replacement to each raw material of product of the present invention and addition assists it will be clearly understood that any improvement in the present invention
Ingredient etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (8)
1. a kind of ammoxidation catalyst of high nitrogen selective, including the coating coated on carrier and carrier, it is characterised in that: institute
Coating is stated to be made of platinum, rare earth modified aluminium oxide, transition metal modified SAPO molecular sieve；The coating load amount be 120~
200g/L；The load capacity of the noble metal platinum is 0.1~10g/ft3；The rare earth modified aluminium oxide middle rare earth and oxygen
The weight ratio for changing aluminium is 0~10:90~100, the weight of the rare earth modified aluminium oxide and transition metal modified SAPO molecular sieve
Than for 10~90:10~90.
2. a kind of ammoxidation catalyst of high nitrogen selective according to claim 1, it is characterised in that: described
Rare earth oxide in rare earth modified aluminium oxide include one of lanthana, cerium oxide, praseodymium oxide, neodymia, yttrium oxide or
It is several；The SAPO molecular sieve, by SiO2、Al2O3、P2O5Composition, SiO2With Al2O3Molar ratio be 0.1~100；The transition
Metal includes one or both of copper and iron；The carrier is through type carrier, and carrier medium is cordierite.
3. a kind of preparation method of the ammoxidation catalyst of high nitrogen selective, which comprises the following steps:
(1) preparation of rare earth modified aluminium oxide: the rare earth metal salt solutions of 0.01~0.1g/mL are added in aluminium oxide, are filled
Divide stirring, then drying calcines, obtains rare earth modified aluminium oxide；
(2) noble metal platinum supported rare earth modified aluminas: being 0.1~10g/ft according to the load capacity of noble metal platinum3, needed for calculating
Noble metal platinum solution；Rare earth modified aluminium oxide, noble metal platinum solution are add to deionized water, are sufficiently stirred, solution is adjusted
PH value obtains the rare earth modified alumina solution of noble metal platinum load to 4~6.5；
(3) preparation method of transition metal modified SAPO is blank SAPO molecular sieve and 0.005mol/L~5mol/L transition metal
Salting liquid is prepared by one or more of hydrothermal crystallizing, ion exchange, infusion process, then by drying, calcining, is obtained
Cross metal-modified molecular sieve；It is calculated with metallic element, transition metal weight accounts for transition metal modified SAPO molecular sieve weight
0.5~3.5%；
(4) it the preparation of slurry: by the modified oxidized aluminum solutions of noble metal platinum supported rare earth, transition metal modified SAPO molecular sieve, glues
Knot agent be add to deionized water, the modified oxidized aluminum solutions of noble metal platinum supported rare earth, transition metal modified SAPO molecular sieve and
The gross mass of binder and the weight ratio of deionized water are 1:0.8~1.4, are sufficiently stirred, form slurry, then ground,
When grinding by slurry partial size D90 control range be 1~25 μm；
(5) coating coating is with catalyst drying, calcining: slurry prepared by step (4) being quantitatively coated on monolithic substrate, so
It is dried, calcined to get ammoxidation catalyst of the invention afterwards；Wherein catalyst coating load amount after calcining is 120
~200g/L；
4. a kind of preparation method of the ammoxidation catalyst of high nitrogen selective according to claim 3, it is characterised in that:
Drying temperature is 120~200 DEG C in step (1), drying time 6~for 24 hours；Maturing temperature is 550~600 DEG C, calcination time 3~
4h。
5. a kind of preparation method of the ammoxidation catalyst of high nitrogen selective according to claim 3, it is characterised in that:
Added noble metal platinum solution is one or more of platinum nitrate, chloroplatinic acid, four ammino platinum of acetic acid in step (2).
6. a kind of preparation method of the ammoxidation catalyst of high nitrogen selective according to claim 3, it is characterised in that:
Blank SAPO molecular sieve is Na in step (3)+Type, H+Type, NH4 +One or more of type；Added transition in step (3)
Metal salt solution is transition metal copper salt solution and transition metal iron salt solutions, and transition metal copper salt solution is copper nitrate, sulfuric acid
One or more of copper, copper acetate, copper chloride, stannous chloride；Transition metal iron salt solutions are ferric nitrate, ferric sulfate, chlorination
One or more of iron, frerrous chloride, ferrous sulfide；Drying temperature is 120~200 DEG C in step (3), drying time 6~
24h；Maturing temperature is 550~600 DEG C, 3~4h of calcination time.
7. a kind of preparation method of the ammoxidation catalyst of high nitrogen selective according to claim 3, it is characterised in that:
The binder of step (4) addition is Al2O3、SiO2、TiO2、ZrO2One or more of powder or colloid；The bonding of addition
Agent is calculated by oxide, and additive amount is the 1~15% of rare earth modified aluminium oxide and cupric molecular sieve powder quality.
8. a kind of preparation method of the ammoxidation catalyst of high nitrogen selective according to claim 3, it is characterised in that:
Coating uses upper feed technique or lower feed technique in step (5)；Drying temperature is 120~200 DEG C, drying time 6~for 24 hours；
Maturing temperature is 500~650 DEG C, and calcination time is 3~4h.
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| CN116440945B (en) * | 2023-03-02 | 2024-04-30 | 昆明贵研催化剂有限责任公司 | Multi-effect catalyst for hydrogen internal combustion engine and preparation method thereof |
| CN116440944A (en) * | 2023-04-27 | 2023-07-18 | 合肥中科弘逸环保科技有限责任公司 | H applied to hydrogen internal combustion engine scene 2 Preparation method and application method of SCR (selective catalytic reduction) catalyst |
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