CN115318303B - Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof - Google Patents
Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof Download PDFInfo
- Publication number
- CN115318303B CN115318303B CN202211027530.6A CN202211027530A CN115318303B CN 115318303 B CN115318303 B CN 115318303B CN 202211027530 A CN202211027530 A CN 202211027530A CN 115318303 B CN115318303 B CN 115318303B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- soot particles
- low temperature
- suspension
- 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 78
- 239000002245 particle Substances 0.000 title claims abstract description 70
- 239000004071 soot Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 49
- 239000000725 suspension Substances 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- BUEPLEYBAVCXJE-UHFFFAOYSA-N [ethenyl-methyl-(trimethylsilylamino)silyl]ethene Chemical compound C(=C)[Si](N[Si](C)(C)C)(C=C)C BUEPLEYBAVCXJE-UHFFFAOYSA-N 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 150000000703 Cerium Chemical class 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 claims description 3
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000002485 combustion reaction Methods 0.000 abstract description 14
- 239000000779 smoke Substances 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052709 silver Inorganic materials 0.000 abstract description 9
- 239000004332 silver Substances 0.000 abstract description 9
- HQFBUALMHFGXCO-UHFFFAOYSA-N cerium oxocobalt Chemical compound [Ce].[Co]=O HQFBUALMHFGXCO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 14
- 229910044991 metal oxide Inorganic materials 0.000 description 14
- 150000004706 metal oxides Chemical class 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012702 metal oxide precursor Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000007084 catalytic combustion reaction Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- MNUSFSHFJMPRIV-UHFFFAOYSA-N [Co].[Ce] Chemical compound [Co].[Ce] MNUSFSHFJMPRIV-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 210000004072 lung Anatomy 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 208000018569 Respiratory Tract disease Diseases 0.000 description 1
- NDCJJBVUAAXANG-UHFFFAOYSA-N [Ce].[Co].[Ag] Chemical compound [Ce].[Co].[Ag] NDCJJBVUAAXANG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000000621 bronchi Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 210000003928 nasal cavity Anatomy 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D49/00—Separating dispersed particles from gases, air or vapours by other methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for removing soot particles of a diesel vehicle at a low temperature and a preparation method thereof. The structured cerium cobalt oxide precursor is prepared through simple hydrothermal reaction, silver nitrate is impregnated and then calcined, and silver species are successfully anchored on the surface of the structured cerium cobalt oxide, so that the catalyst for removing soot particles of the diesel vehicle at low temperature is successfully prepared. Based on the enhanced specific surface area, more active sites and a special oxygen vacancy structure of the structured cerium cobalt oxide, the structured cerium cobalt oxide and silver species on the surface generate a synergistic effect, enhance the reaction of the carbon smoke particles on the surface and can reduce the combustion temperature of the carbon smoke particles to 325 ℃; the catalyst has high catalytic activity on the carbon smoke particles under the condition of loose contact with the carbon smoke particles and no existence of nitrogen oxides.
Description
Technical Field
The invention belongs to the technical field of catalytic combustion, and particularly relates to a catalyst for removing soot particles of a diesel vehicle at a low temperature and a preparation method thereof.
Background
The diesel vehicle has the advantages of high efficiency, heat utilization rate, low cost, strong engine horsepower, low carbon dioxide emission, wide application range and the like, is widely focused under the current situation that crude oil is increasingly exhausted and carbon dioxide emission requirements are gradually strict, and diesel oil is one of the trend directions of automobiles under the national energy-saving emission-reduction treatment policy, but the emission of the diesel vehicle also brings adverse effects to the treatment of the atmospheric environment and the health of residents in China. The components of pollutants in the tail gas discharged by the diesel vehicle are very complex, and the pollutants include soot particles, carbon monoxide, hydrocarbon, oxynitride and the like. Wherein, the carbon smoke particles are the pollutant which is the most harmful and difficult to eliminate, and the granularity range is 0.05-1 mu m. Because the particle diameter of carbon smoke particles in the tail gas of the diesel vehicle is smaller, particularly small particles with the particle diameter smaller than 2.5 mu m are not easy to be blocked by nasal cavity villus, and can directly enter bronchi after being inhaled into the lung, so that the gas exchange of the lung is affected, and a series of respiratory tract and cardiovascular diseases are caused. At the same time, soot particles are also an important factor in causing haze.
Currently, the air pollution control work attracts much attention in many countries, and the country is also beginning to apply to the treatment of air pollution. In order to meet the increasingly strict regulatory requirements, three main methods for solving the soot particle pollution of diesel vehicle emission are: firstly, the used fuel is improved or a novel environment-friendly alternative fuel is used; secondly, improving the engine of the diesel vehicle; and thirdly, an exhaust aftertreatment system is improved, and a tail gas purifying system is additionally arranged. The third method is generally considered to be most effective based on technical and economic considerations. In the actual exhaust gas aftertreatment technology, the technology of combining a solid particle catcher with a catalyst is the key point of current research, wherein the development of the catalyst with excellent performance is the core.
CN 107159231a discloses a preparation method of a monocrystal supported catalyst for eliminating soot particles of diesel vehicles at low temperature, which is prepared by immersing monocrystal alpha-phase manganese sesquioxide cubes in a metal salt solution, and the catalyst has the advantages of low cost, simple preparation method, convenience for industrialization, high catalytic activity and capability of well reducing the combustion temperature of soot particles of diesel vehicles. CN 103212414A discloses a preparation method of a supported silver catalyst for reducing the combustion temperature of soot particles, the catalyst comprises an active component and a carrier, the active component is silver, the carrier is cerium dioxide or cerium-based composite oxide, the silver loading is 1% -20% of the carrier mass, the catalyst has good oxidation activity in the combustion of soot particles, and the temperature of the soot particles in the combustion process can be reduced from 642 ℃ to 400 ℃ or so to reach the operating temperature range of a diesel engine. CN 106824161A discloses a preparation method of a micron sheet-shaped soot combustion catalyst, which is prepared by mixing a solution containing a cerium source or a lanthanum source with an alkaline solution, precipitating at low temperature, and calcining insoluble substances, wherein the catalyst has a micron sheet-shaped rare earth metal oxide catalyst which has good crystallization and does not contain any noble metal, and has a micron sheet-shaped morphology, can be in high-efficiency contact with carbon particles, has excellent catalytic oxidation activity, and has potential application prospects in the aspect of combustion degradation of solid pollutants.
Catalysts commonly used in the art for soot particle oxidation, such as: ceO (CeO) 2 Base compounds, perovskite oxides, noble metal based catalysts, etc., are disadvantageous for contact of active sites with carbon particles due to lack of pore structure, high cost of noble metals and easy toxicity, resulting in low catalyst activity and easy deactivation, which limits industrial application of catalysts for oxidation of soot particles.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a catalyst for removing soot particles of a diesel vehicle at a low temperature and a preparation method thereof. The catalyst has good effect on the catalytic oxidation of the soot particles under loose contact, can effectively convert the soot particles into carbon dioxide, and can remarkably reduce the temperature of the thermal oxidation of the soot particles.
In order to achieve the above object, the present invention provides a method for preparing a catalyst for removing soot particles of a diesel vehicle at a low temperature, comprising the steps of:
step 1: stirring the soluble metal salt and the ethanol water solution at the stirring rate of 300-500 r/min to form a solution I; adjusting the pH value of the solution I to 9.0-11.0 by using an alkaline aqueous solution, and continuously stirring for 0.5-2 h after adjusting the pH value to obtain a solution II; carrying out hydrothermal reaction on the solution II at 160-180 ℃ for 6-15 h, naturally cooling to 25-30 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80-120 ℃ for 6-12 h to obtain solid powder;
step 2: dispersing the solid powder obtained in the step 1 in water, and forming a suspension a under the conditions that the ultrasonic power is 50-200W, the frequency is 20-130 kHz, the temperature is 20-40 ℃ and the ultrasonic treatment is carried out for 20-60 min; adding silver nitrate into a suspension a stirred at a stirring rate of 300-500 r/min, reacting for 0.5-2 h to obtain a suspension b, stopping stirring, transferring the suspension b to 90-120 ℃ and keeping for 12-18 h, evaporating the water of the suspension b, collecting solid matters, and calcining the solid matters at 400-600 ℃ for 2-5 h; the calcined solid matter is crushed and screened by a 300-500 mesh screen, and the powder under the screen is collected to obtain the catalyst for eliminating the soot particles of the diesel vehicle.
Preferably, the mass ratio of the soluble metal salt to the ethanol aqueous solution in the step 1 is 1: (30-50).
The soluble metal salt is soluble cobalt salt or soluble cerium salt; the soluble cobalt salt is one of cobalt nitrate hexahydrate (II), cobalt acetate tetrahydrate (II) and cobalt chloride hexahydrate (II); the soluble cerium salt is one of cerium (III) nitrate hexahydrate and cerium (III) chloride heptahydrate.
The mass fraction of the ethanol aqueous solution is 60-80%.
The alkaline aqueous solution is one of an aqueous ammonia solution, an aqueous sodium hydroxide solution, an aqueous sodium bicarbonate solution and an aqueous sodium carbonate solution which are 1-3 mol/L.
The catalytic oxidation performance of a single metal oxide catalyst on soot particles is primarily affected by the redox capacity of the metal oxide, the mobility of the surface active species, and the contact with the soot particles. Under general conditions, the catalytic combustion performance of a single metal oxide catalyst on the carbon soot particles is not obviously improved, the carbon soot particles can be effectively combusted only by reaching more than 500 ℃, and the selectivity of the catalytic combustion to form carbon dioxide is also not ideal. The composite metal oxide catalyst is a catalyst formed by compounding two or more metal elements, and the catalytic oxidation performance of the catalyst on soot particles is mainly related to the self-catalytic activity of the metal oxide and the synergistic catalytic effect among different components. Many studies have shown that composite metal oxides benefit from a one-component metal oxide to metal oxide phase change, enhanced oxygen species storage in the structure, and synergistic interaction between the components, which can significantly improve the catalytic combustion performance of the catalyst.
More preferably, the mass ratio of the soluble cobalt salt to the soluble cerium salt in the soluble metal salt in the step 1 is 1: (3-5).
Preferably, the mass ratio of the solid powder to the water in the step 2 is (0.02-0.05): 1, a step of; the mass ratio of the added silver nitrate to the solid powder is (1:10) - (1:30).
The catalytic properties of metal oxides are largely dependent on their structure. In the process of preparing metal oxide by using water heating or solvent heating, the structure regulating substance in the precursor solution can be used for preparing metal oxides with various morphologies. Surfactants are the most commonly used structure-modifying substances. However, surfactants are difficult to remove, and some surfactants with specific functions are expensive. The low molecular sugar can generate polymerization reaction under the temperature and pressure of hydrothermal or solvothermal to generate oligomer, and the oligomer has structure regulation and control effect on metal ions in a liquid phase environment. Therefore, sugar is added into the metal precursor solution, and the formed metal oxidation structure can be regulated and controlled under certain reaction conditions.
Some low-molecular nitrogen-containing substances have strong coordination to metal ions in a liquid phase environment, can regulate and control the growth rate and direction of crystal nuclei of early-formed metal oxide precursors, and can also play a role in regulating and controlling the structure of metal oxidation.
Further preferably, the preparation method of the catalyst for removing soot particles of the diesel vehicle at low temperature comprises the following steps:
step 1: stirring a soluble cobalt salt, a soluble cerium salt, sugar and ethanol water solution at a stirring rate of 300-500 r/min to form a solution I; adjusting the pH value of the solution I to 9.0-11.0 by using an alkaline aqueous solution, adding a nitrogen-containing substance after adjusting the pH value, and continuously stirring for 0.5-2 h to obtain a solution II; and carrying out hydrothermal reaction on the solution II for 6-15 h at 160-180 ℃, naturally cooling to 25-30 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80-120 ℃ for 6-12 h to obtain solid powder.
Step 2: dispersing the solid powder obtained in the step 1 in water, and forming a suspension a under the conditions that the ultrasonic power is 50-200W, the frequency is 20-130 kHz, the temperature is 20-40 ℃ and the ultrasonic treatment is carried out for 20-60 min; adding silver nitrate into a suspension a stirred at a stirring rate of 300-500 r/min, reacting for 0.5-2 h to obtain a suspension b, stopping stirring, keeping the suspension b at 90-120 ℃ for 12-18 h, evaporating the water of the suspension b, collecting solid matters, and calcining the solid matters at 400-600 ℃ for 2-5 h; the calcined solid matter is crushed and screened by a 300-500 mesh screen, and the powder under the screen is collected to obtain the catalyst for eliminating the soot particles of the diesel vehicle.
Preferably, the mass ratio of the soluble cerium salt, the soluble cobalt salt, the soluble cerium salt sugar and the ethanol aqueous solution added in the step 1 is (0.2-2): (0.2-2): (0.1-0.5): (30-50).
The soluble cobalt salt is one of cobalt nitrate hexahydrate (II), cobalt acetate tetrahydrate (II) and cobalt chloride hexahydrate (II), and the soluble cerium salt is one of cerium nitrate hexahydrate (III) and cerium chloride heptahydrate (III).
The sugar is one or a combination of two or more of glucose, sucrose and lactose.
The mass fraction of the ethanol aqueous solution is 60-80%.
The alkaline aqueous solution is one of an aqueous ammonia solution, an aqueous sodium hydroxide solution, an aqueous sodium bicarbonate solution and an aqueous sodium carbonate solution which are 1-3 mol/L.
The mass ratio of the nitrogen-containing substance to the soluble metal salt is (2-5): 1, a step of; the nitrogen-containing substance is one or the combination of two or more of hexamethylenetetramine, urea, glycine, ethylenediamine, hexamethyldisilazane and tetramethyl divinyl disilazane.
Preferably, the mass ratio of the solid powder to the water in the step 2 is (0.02-0.05): 1, a step of; the mass ratio of the added silver nitrate to the solid powder is (1:10) - (1:30).
The invention has the beneficial effects that:
(1) The preparation method prepares the structured cerium cobalt oxide precursor through simple hydrothermal reaction, impregnates silver nitrate, then calcines the precursor, successfully anchors silver species on the surface of the structured cerium cobalt oxide, successfully prepares the catalyst for removing soot particles of diesel vehicles at low temperature, has simple preparation process, easily obtained raw materials, no toxicity or low toxicity, and is suitable for industrial scale-up production.
(2) The carbon smoke particle catalyst prepared by the invention can effectively convert carbon smoke particles into carbon dioxide for simulating the catalysis of the carbon smoke particles of the tail gas of the diesel vehicle; based on the synergistic effect of structured cerium oxide, cobaltosic oxide and silver, the catalyst prepared by the invention has high catalytic activity on the carbon smoke particles under the conditions of loose contact state with the carbon smoke particles and no existence of nitrogen oxides; and can reduce the combustion temperature of the soot particles to 325 ℃.
Drawings
Fig. 1 is a scanning electron microscope image of the catalyst for removing soot particles of a diesel vehicle at low temperature prepared by the present invention, (a) example 3, (B) example 4, (C) example 5, and (D) example 6.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1A method for preparing a soot particulate catalyst
(1) 3.5g of cobalt nitrate hexahydrate is dissolved in 100g of ethanol aqueous solution with the mass fraction of 70% at the stirring rate of 300r/min to form solution I; adjusting the pH value of the solution I to 9.5 by using 2mol/L aqueous ammonia solution, and continuously stirring for 1h at a stirring rate of 300r/min to form a solution II; transferring the solution II to a polytetrafluoroethylene liner, loading into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reaction for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80 ℃ in a constant temperature oven for 6 hours to obtain solid powder;
(2) Dispersing 5g of the solid powder obtained in the step 1 in a beaker containing 100g of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50kHz and the temperature of 25 ℃ to obtain a suspension a; dissolving 0.2g of silver nitrate in a suspension a stirred at a stirring rate of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker containing the suspension b to a constant temperature oven, drying at 120 ℃ for 12h, evaporating the moisture of the suspension b, collecting the residual solid matters, and placing the solid matters under a muffle furnace at 550 ℃ for calcination for 2h; crushing the calcined solid material, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver-doped tricobalt tetraoxide, namely the catalyst prepared in the embodiment.
Example 2A method for preparing a soot particulate catalyst
(1) 3.5g of cerium nitrate hexahydrate is dissolved in 100g of ethanol aqueous solution with the mass fraction of 70% at the stirring rate of 300r/min to form a solution I; adjusting the pH value of the solution I to 9.5 by using 2mol/L aqueous ammonia solution, and continuously stirring for 1h at a stirring rate of 300r/min to form a solution II; transferring the solution II to a polytetrafluoroethylene liner, loading into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reaction for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80 ℃ in a constant temperature oven for 6 hours to obtain solid powder;
(2) Dispersing 5g of the solid powder obtained in the step 1 in a beaker containing 100g of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50kHz and the temperature of 25 ℃ to obtain a suspension a; dissolving 0.2g of silver nitrate in a suspension a stirred at a stirring rate of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker containing the suspension b to a constant temperature oven, drying at 120 ℃ for 12h, evaporating the moisture of the suspension b, collecting the residual solid matters, and placing the solid matters under a muffle furnace at 550 ℃ for calcination for 2h; and (3) crushing the calcined solid matters, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain silver-doped cerium oxide, namely the catalyst prepared in the embodiment.
Example 3A method for preparing a soot particulate catalyst
(1) 2.8g of cerium nitrate hexahydrate and 0.7g of cobalt nitrate hexahydrate are dissolved in 100g of ethanol aqueous solution with the mass fraction of 70% at the stirring rate of 300r/min to form a solution I; adjusting the pH value of the solution I to 9.5 by using 2mol/L aqueous ammonia solution, and continuously stirring for 1h at a stirring rate of 300r/min to form a solution II; transferring the solution II to a polytetrafluoroethylene liner, loading into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reaction for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80 ℃ in a constant temperature oven for 6 hours to obtain solid powder;
(2) Dispersing 5g of the solid powder obtained in the step 1 in a beaker containing 100g of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50kHz and the temperature of 25 ℃ to obtain a suspension a; dissolving 0.2g of silver nitrate in a suspension a stirred at a stirring rate of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker containing the suspension b to a constant temperature oven, drying at 120 ℃ for 12h, evaporating the moisture of the suspension b, collecting the residual solid matters, and placing the solid matters under a muffle furnace at 550 ℃ for calcination for 2h; crushing the calcined solid material, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain the silver-doped cobalt-cerium bimetallic oxide, namely the catalyst prepared in the embodiment.
Example 4A method for preparing a soot particulate catalyst
(1) 2.8g of cerium nitrate hexahydrate, 0.7g of cobalt nitrate hexahydrate and 1g of glucose are dissolved in 100g of ethanol aqueous solution with the mass fraction of 70% under the stirring rate of 300r/min to form a solution I; adjusting the pH value of the solution I to 9.5 by using 2mol/L aqueous ammonia solution, and continuously stirring for 1h at a stirring rate of 300r/min to form a solution II; transferring the solution II to a polytetrafluoroethylene liner, loading into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reaction for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80 ℃ in a constant temperature oven for 6 hours to obtain solid powder;
(2) Dispersing 5g of the solid powder obtained in the step 1 in a beaker containing 100g of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50kHz and the temperature of 25 ℃ to obtain a suspension a; dissolving 0.2g of silver nitrate in a suspension a stirred at a stirring rate of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker containing the suspension b to a constant temperature oven, drying at 120 ℃ for 12h, evaporating the moisture of the suspension b, collecting the residual solid matters, and placing the solid matters under a muffle furnace at 550 ℃ for calcination for 2h; crushing the calcined solid material, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain the flaky silver cobalt-doped cerium bimetallic oxide, namely the catalyst prepared in the embodiment.
Example 5A method for preparing a soot particulate catalyst
(1) 2.8g of cerium nitrate hexahydrate and 0.7g of cobalt nitrate hexahydrate are dissolved in 100g of ethanol aqueous solution with the mass fraction of 70% at the stirring rate of 300r/min to form a solution I; adjusting the pH of the solution I to 9.5 by using 2mol/L aqueous ammonia solution, adding 8g of tetramethyl divinyl disilazane, and continuously stirring at a stirring rate of 300r/min for 1h to form a solution II; transferring the solution II to a polytetrafluoroethylene liner, loading into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reaction for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80 ℃ in a constant temperature oven for 6 hours to obtain solid powder;
(2) Dispersing 5g of the solid powder obtained in the step 1 in a beaker containing 100g of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50kHz and the temperature of 25 ℃ to obtain a suspension a; dissolving 0.2g of silver nitrate in a suspension a stirred at a stirring rate of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker containing the suspension b to a constant temperature oven, drying at 120 ℃ for 12h, evaporating the moisture of the suspension b, collecting the residual solid matters, and placing the solid matters under a muffle furnace at 550 ℃ for calcination for 2h; crushing the calcined solid material, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain the flaky silver cobalt-doped cerium bimetallic oxide, namely the catalyst prepared in the embodiment.
Example 6 preparation of a soot particulate catalyst
(1) 2.8g of cerium nitrate hexahydrate, 0.7g of cobalt nitrate hexahydrate and 1g of glucose are dissolved in 100g of ethanol aqueous solution with the mass fraction of 70% under the stirring rate of 300r/min to form a solution I; adjusting the pH of the solution I to 9.5 by using 2mol/L aqueous ammonia solution, adding 8g of tetramethyl divinyl disilazane, and continuously stirring at a stirring rate of 300r/min for 1h to form a solution II; transferring the solution II to a polytetrafluoroethylene liner, loading into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reaction for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80 ℃ in a constant temperature oven for 6 hours to obtain solid powder;
(2) Dispersing 5g of the solid powder obtained in the step 1 in a beaker containing 100g of water, and carrying out ultrasonic treatment for 30min at the ultrasonic power of 100W, the frequency of 50kHz and the temperature of 25 ℃ to obtain a suspension a; dissolving 0.2g of silver nitrate in a suspension a stirred at a stirring rate of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker containing the suspension b to a constant temperature oven, drying at 120 ℃ for 12h, evaporating the moisture of the suspension b, collecting the residual solid matters, and placing the solid matters under a muffle furnace at 550 ℃ for calcination for 2h; and (3) crushing the calcined solid matters, sieving with a 300-mesh sieve, and collecting powder under the sieve to obtain the silver cobalt-cerium doped bimetallic oxide with the three-dimensional interconnected porous structure, namely the catalyst prepared in the embodiment.
Test example 1 morphology of catalyst
The catalysts prepared in example 3, example 4, example 5 and example 6 were characterized by scanning electron microscopy, and the results are shown in fig. 1.
For example 3, example 4, implementationThe catalysts prepared in example 5 and example 6 were tested for specific surface area and pore structure. The specific surface area was calculated using Brunauer-Emmett-Teller (BET) model, and the pore size (D) was calculated using Barren-Joyner-Halenda (BJH) model p ) Distribution. The results are shown in Table 1.
TABLE 1 results of specific surface area test
| BET specific surface area (m) 2 /g) | D p (nm) | |
| Example 3 | 68.7 | 12.8 |
| Example 4 | 83.6 | 14.6 |
| Example 5 | 98.1 | 18.3 |
| Example 6 | 127.3 | 25.6 |
It can be seen from fig. 1 that example 3, in which glucose and tetramethyl divinyl disilazane were not added, exhibited a lump shape; example 4, prepared with the addition of glucose, and example 5, prepared with the addition of tetramethyl divinyl disilazane, exhibited a distinct lamellar structure. This is because under hydrothermal conditions, the coordination attraction of the oligomer formed by polymerization of glucose and tetramethyl divinyl disilazane mediates the nucleation and growth of the metal oxide precursor in the planar direction. In addition, example 6, prepared by adding glucose and tetramethyl divinyl disilazane, exhibited a distinct three-dimensional interconnected porous structure with distinct macropores (> 50 nm) present. This suggests that glucose and tetramethyl divinyl disilazane have a synergistic modulating effect on the structure of the complex metal oxide. It is possible that the polymerization of glucose into oligomer at high temperature has an adjusting effect on the structure of the metal oxide precursor, and the crystal nucleus of the metal oxide precursor can be polymerized into a sheet shape and continuously grow, and the sheet-shaped metal oxide precursor is formed after the hydrothermal reaction is finished; the addition of the tetramethyl divinyl disilazane enables the metal oxide precursor crystal nucleus to grow rapidly along with the layered structure coordinated by the alcohol and the metal ions, the flaky structure further grows along with the reaction, the three-dimensional porous structured metal oxide precursor is formed through self-assembly polymerization, and the silver-doped three-dimensional porous structured metal oxide catalyst is prepared through final calcination treatment.
The specific surface area test is consistent with the scanning electron microscope test result, and the specific surface area and the pore size distribution of the catalyst are improved by adding glucose and tetramethyl divinyl disilazane. Example 6 the unique three-dimensional interconnected porous structure can accommodate more soot particles, provide more active sites, and may be more suitable for catalytic combustion of soot particles.
Test example 2 catalytic Activity of the catalyst
The catalytic activity evaluation of the catalyst is carried out by a temperature programming oxidation technology, a tubular heating furnace is utilized for temperature programming, oxygen, nitric oxide, water vapor and nitrogen are continuously introduced into the reactor, and the gas at the outlet is tested by a Fourier infrared spectrum gas tester.
Mixing 5mg of carbon smoke particles with 50mg of catalyst to form loose contact, diluting the mixed sample with 100mg of inert silicon dioxide, and placing the diluted sample into a quartz tube with the inner diameter of 10 mm; and placing the quartz tube in a temperature programming oxidation reactor, and carrying out temperature programming and reaction temperature control through a tubular electric heating furnace in the reactor. The temperature range of the temperature programming experiment is 50-650 ℃, the temperature increasing rate is 2.5 ℃/min, and the temperature is maintained for 30min after reaching the target temperature. The catalytic tests of the soot particles were carried out in 2 different atmospheres, respectively, (1) 10% oxygen, 10% water vapor, nitrogen balance gas, total gas flow 100mL/min, (2) 1000ppm nitric oxide, 10% water vapor, 10% oxygen and nitrogen balance gas, total gas flow 100mL/min.
The combustion process of the soot particles was monitored using an on-line mass spectrum, with an m/z=44 signal for monitoring the amount of carbon dioxide and an m/z=28 signal for monitoring the amount of carbon monoxide. The selectivity of catalytic oxidation of soot particles to carbon dioxide is determined by the following equation:
in the middle ofAnd C CO The carbon dioxide concentration and the carbon monoxide concentration of the outlet are respectively; />Indicating the selectivity to carbon dioxide.
The activity evaluation indexes of the catalyst for catalyzing the combustion of the particulate matters are as follows: the selectivity of carbon dioxide; the reaction temperatures at which the soot particle conversion rates were 10%, 50% and 90%, respectively, are denoted as T 10 、T 50 、T 90 。
The results of the catalytic combustion of soot particles by the catalysts prepared in the examples of the present invention are shown in table 1 below.
TABLE 1 results of catalyst performance under an atmosphere of 10% oxygen, 10% steam and nitrogen balance
As can be seen from the results of examples 1 to 3, the catalytic combustion performance of the soot particles of the silver-doped ceria catalyst is better than that of the silver-doped tricobalt tetraoxide catalyst, and the selectivity of the two catalysts for oxidizing combustion of the soot particles to carbon dioxide is not ideal; and the selectivity of carbon dioxide of the silver-doped cobalt-cerium bimetallic oxide catalyst prepared in the embodiment 3 is obviously improved, and the temperature of carbon smoke oxidation combustion is also obviously reduced. This is probably because cobalt is successfully incorporated into the unit cell structure of ceria and forms a solid solution, reducing the grain size of ceria; the introduction of cobalt also increases oxygen vacancies and defects of the ceria crystals, increasing the reactive sites.
From the test results of examples 3-6, it can be seen that the addition of glucose and tetramethyl divinyl disilazane during the preparation process increases the performance of the catalyst and decreases the temperature required for combustion of the soot particles. This is probably because the polymerization of glucose into oligomer at high temperature has an adjusting effect on the structure of the metal oxide precursor, and the crystal nucleus of the metal oxide precursor can be polymerized into a sheet shape and continuously grow, and the sheet-shaped metal oxide precursor is formed after the hydrothermal reaction is finished; the addition of the tetramethyl divinyl disilazane enables the metal oxide precursor crystal nucleus to grow rapidly along with the layered structure coordinated by the alcohol and the metal ions, the flaky structure further grows along with the reaction, the three-dimensional porous structured metal oxide precursor is formed through self-assembly polymerization, and the silver-doped three-dimensional porous structured metal oxide catalyst is prepared through final calcination treatment. Such a three-dimensional porous structure facilitates adsorption of soot particles on the catalyst surface and further promotes the progress of the catalytic reaction.
In order to further approach the practical use environment, the catalyst prepared in the embodiment of the invention is subjected to catalytic test under the conditions of 1000ppm of nitric oxide, 10% of water vapor, 10% of oxygen and nitrogen balance gas and total gas flow of 100mL/min, and the results are shown in Table 2. It can be seen that the presence of nitric oxide enhances the performance of the catalyst, since part of the nitric oxide is oxidized by the catalyst to nitrogen dioxide, which has a stronger catalytic capacity than oxygen, enhancing the oxidation of the soot particles. These results also demonstrate that example 6 of the present invention has good catalytic performance for simulating the oxidative combustion of soot particles in diesel exhaust, and can effectively convert soot particles to carbon dioxide at about 400 ℃.
TABLE 2 Performance results of catalysts under an atmosphere of 1000ppm nitric oxide, 10% steam, 10% oxygen, nitrogen balance
Claims (7)
1. A method for preparing a catalyst for removing soot particles of a diesel vehicle at a low temperature, which is characterized by comprising the following steps:
step 1: stirring a soluble cobalt salt, a soluble cerium salt, sugar and ethanol water solution at a stirring rate of 300-500 r/min to form a solution I; adjusting the pH value of the solution I to 9.0-11.0 by using an alkaline aqueous solution, then adding a nitrogen-containing substance, and continuously stirring for 0.5-2 h to obtain a solution II; carrying out hydrothermal reaction on the solution II at 160-180 ℃ for 6-15 h, naturally cooling to 25-30 ℃, filtering insoluble substances, washing with ethanol and water three times respectively, and drying at 80-120 ℃ for 6-12 h to obtain solid powder;
step 2: dispersing the solid powder obtained in the step 1 in water, and forming a suspension a under the conditions that the ultrasonic power is 50-200W, the frequency is 20-130 kHz, the temperature is 20-40 ℃ and the ultrasonic treatment is carried out for 20-60 min; adding silver nitrate into a suspension a stirred at a stirring rate of 300-500 r/min, reacting for 0.5-2 h to obtain a suspension b, stopping stirring, keeping the suspension b at 90-120 ℃ for 12-18 h, evaporating the water of the suspension b, collecting solid matters, and calcining the solid matters at 400-600 ℃ for 2-5 h; crushing the calcined solid matters, sieving with a 300-500 mesh sieve, and collecting powder under the sieve to obtain the catalyst for removing the soot particles of the diesel vehicle at low temperature;
the sugar is one or the combination of two or more of glucose, sucrose and lactose;
the mass ratio of the nitrogen-containing substance to the soluble metal salt is (2-5): 1, a step of; the nitrogen-containing substance is one or the combination of two or more of hexamethylenetetramine, urea, glycine, ethylenediamine, hexamethyldisilazane and tetramethyl divinyl disilazane.
2. The method for preparing the catalyst for removing soot particles of a diesel vehicle at a low temperature according to claim 1, wherein the soluble cobalt salt is one of cobalt nitrate hexahydrate (ii), cobalt acetate tetrahydrate (ii) and cobalt chloride hexahydrate (ii); the soluble cerium salt is one of cerium (III) nitrate hexahydrate and cerium (III) chloride heptahydrate.
3. The method for preparing the catalyst for removing soot particles of diesel vehicles at low temperature according to claim 1, wherein the mass fraction of the aqueous ethanol solution is 60-80%.
4. The method for preparing the catalyst for removing soot particles of a diesel vehicle at a low temperature according to claim 1, wherein the alkaline aqueous solution is one of aqueous ammonia solution, aqueous sodium hydroxide solution, aqueous sodium bicarbonate solution and aqueous sodium carbonate solution.
5. The method for preparing the catalyst for removing soot particles of diesel vehicles at low temperature according to claim 2, wherein the mass ratio of the soluble cerium salt, the soluble cobalt salt, the sugar and the ethanol aqueous solution in the step 1 is (0.2-2): (0.2-2): (0.1-0.5): (30-50).
6. The method for preparing the catalyst for removing soot particles of diesel vehicles at low temperature according to claim 2, wherein the mass ratio of the solid powder to water in the step 2 is (0.02-0.05): 1, a step of; the mass ratio of the added silver nitrate to the solid powder is (1:10) - (1:30).
7. A catalyst for removing soot particles from diesel vehicles at low temperature, which is prepared by the preparation method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211027530.6A CN115318303B (en) | 2022-08-25 | 2022-08-25 | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211027530.6A CN115318303B (en) | 2022-08-25 | 2022-08-25 | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115318303A CN115318303A (en) | 2022-11-11 |
| CN115318303B true CN115318303B (en) | 2024-03-01 |
Family
ID=83928487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211027530.6A Active CN115318303B (en) | 2022-08-25 | 2022-08-25 | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115318303B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116790160B (en) * | 2023-08-02 | 2024-01-23 | 胜利油田固邦石油装备有限责任公司 | Environment-friendly paint with formaldehyde removing function |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1541219A1 (en) * | 2003-12-08 | 2005-06-15 | Ford Global Technologies, LLC, A subsidary of Ford Motor Company | Method and device for removal of NOx and particulate matter |
| CN103212414A (en) * | 2013-04-15 | 2013-07-24 | 厦门大学 | Supported silver catalyst for reducing soot particle burning temperature and preparation method |
| CN104707623A (en) * | 2013-12-16 | 2015-06-17 | 裴振昭 | Method for preparing catalyst for catalytic combustion of methane |
| CN105498782A (en) * | 2016-01-07 | 2016-04-20 | 昆明理工大学 | Preparing method for cubic morphology nano-composite metal oxide catalyst CeO2-Co3O4 |
| CN105597781A (en) * | 2016-02-01 | 2016-05-25 | 厦门大学 | Combustion catalyst for carbon particulate matters and preparation method thereof |
| CN107008409A (en) * | 2017-04-25 | 2017-08-04 | 四川师范大学 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
| CN108568297A (en) * | 2017-03-08 | 2018-09-25 | 天津大学 | Cerium base catalyst with core-casing structure and preparation method thereof |
| CN110732321A (en) * | 2019-09-18 | 2020-01-31 | 沈阳化工大学 | Preparation method of silicotungstic acid modified cerium dioxide catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9108155B2 (en) * | 2011-10-10 | 2015-08-18 | Hyundai Motor Company | Non-PGM catalyst for burning carbon soot, and filtration filter and exhaust gas post-processing apparatus using the same |
| US20200122128A1 (en) * | 2018-10-19 | 2020-04-23 | Korea Institute Of Energy Research | Method for producing aliphatic linear primary alcohols |
-
2022
- 2022-08-25 CN CN202211027530.6A patent/CN115318303B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1541219A1 (en) * | 2003-12-08 | 2005-06-15 | Ford Global Technologies, LLC, A subsidary of Ford Motor Company | Method and device for removal of NOx and particulate matter |
| CN103212414A (en) * | 2013-04-15 | 2013-07-24 | 厦门大学 | Supported silver catalyst for reducing soot particle burning temperature and preparation method |
| CN104707623A (en) * | 2013-12-16 | 2015-06-17 | 裴振昭 | Method for preparing catalyst for catalytic combustion of methane |
| CN105498782A (en) * | 2016-01-07 | 2016-04-20 | 昆明理工大学 | Preparing method for cubic morphology nano-composite metal oxide catalyst CeO2-Co3O4 |
| CN105597781A (en) * | 2016-02-01 | 2016-05-25 | 厦门大学 | Combustion catalyst for carbon particulate matters and preparation method thereof |
| CN108568297A (en) * | 2017-03-08 | 2018-09-25 | 天津大学 | Cerium base catalyst with core-casing structure and preparation method thereof |
| CN107008409A (en) * | 2017-04-25 | 2017-08-04 | 四川师范大学 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
| CN110732321A (en) * | 2019-09-18 | 2020-01-31 | 沈阳化工大学 | Preparation method of silicotungstic acid modified cerium dioxide catalyst |
Non-Patent Citations (8)
| Title |
|---|
| Ag supported on CeO2 with different morphologies for the catalytic oxidation of HCHO;Yu Lian 等;《CHEMICAL ENGINEERING JOURNAL》;第334卷;第2481页2.1.1、2.1.2 * |
| Ag/Co-Ce复合氧化物在O2及NOx气氛中催化燃烧碳烟的性能:Ag的作用;邹谷初 等;《催化学报》;第38卷(第3期);第564-573页 * |
| Bifunctional One-Dimensional Hierarchical Nanostructures Composed of Cobalt Sulfide Nanoclusters on Carbon Nanotubes Backbone for Dye-Sensitized Solar Cells and Supercapacitors;Lin Jeng Yu 等;《JOURNAL OF PHYSICAL CHEMISTRY C》;第118卷(第2期);第823-830页 * |
| Chemisorbed Superoxide Species Enhanced the High Catalytic Performance of Ag/Co3O4 Nanocubes for Soot Oxidation;Chen Longwen 等;《ACS APPLIED MATERIALS & INTERFACES》;第13卷(第18期);第21436页摘要部分、左栏第2段、右栏第1段 * |
| Hydrogen Production from Steam Reforming of Acetic Acid as a Model Compound of the Aqueous Fraction of Microalgae HTL Using Co-M/SBA-15 (M: Cu, Ag, Ce, Cr) Catalysts;Megia Pedro J. 等;《CATALYSTS》;第9卷(第12期);第1-19页 * |
| Soot combustion over Ag catalysts supported on shape-controlled CeO2;Wang Wei 等;《CATALYSIS TODAY》;第376卷;第9-18页 * |
| Synthesis of a CeO2/Co3O4 catalyst with a remarkable performance for the soot oxidation reaction;Medina J. C. 等;《CATALYSIS SCIENCE & TECHNOLOGY》;第10卷(第3期);第853-863页 * |
| 改性Ag基催化剂用于碳烟颗粒催化氧化的研究;温兆军;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第7期);B014-540 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115318303A (en) | 2022-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107362807B (en) | Mn/Co-based low-temperature SCO catalyst and preparation method thereof | |
| CN108744953B (en) | Application method of OMS-2 and/or metal-doped OMS-2 catalytic flue gas denitration | |
| CN109772465B (en) | Preparation method of water-soluble carbon dot modified perovskite type catalytic material | |
| CN107456964A (en) | For the extra specific surface area perovskite type composite oxide catalyst of hydrocarbon low-temperature oxidation and its preparation | |
| CN106268787A (en) | A kind of samarium doping MnOxlow-temperature SCR catalyst and its preparation method and application | |
| CN110681382B (en) | MOF-cobalt-based metal oxide catalyst for catalytic oxidation of toluene and preparation method thereof | |
| CN108816239B (en) | Supported catalyst, preparation method and application thereof | |
| CN110354799A (en) | A kind of cerium dioxide nano material possessing good low temperature NOx storage capacity | |
| WO2009094891A1 (en) | A cu-ce-al catalyst for removing soot particles and nox simultaneously and its preparation method | |
| CN113713838B (en) | Preparation method of integral oxidation type catalyst for diesel vehicle | |
| CN108926911A (en) | A kind of preparation method of denitration demercuration monoblock type filtrate | |
| CN115318303B (en) | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof | |
| CN110124710B (en) | Composite metal oxide catalyst and preparation method thereof | |
| CN109772288B (en) | Surface cerium-rich nano cerium-zirconium composite oxide and preparation and application thereof | |
| CN108404930A (en) | A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid | |
| CN108579756B (en) | Laminaria-shaped Mn-Fe bimetal oxide loaded CeO2Catalyst, preparation method and application | |
| CN115430433B (en) | Catalyst with high-efficiency activity and preparation method thereof | |
| CN113262780A (en) | High-activity and high-stability manganese-based carbon smoke catalyst and preparation method and application thereof | |
| CN110697768A (en) | Mesoporous TiO 22Material, catalyst, preparation method of material and catalyst, and denitration method | |
| CN114733514B (en) | Integral catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies, and preparation method and application thereof | |
| CN106799225A (en) | A kind of potassium support type soot combustion catalyst and its preparation method and application | |
| CN110586118A (en) | Magnetic iron-based catalyst for selective catalytic reduction denitration and preparation method thereof | |
| JP2006043683A (en) | Catalyst carrier and its manufacturing method and catalyst for cleaning exhaust gas | |
| CN111250078B (en) | MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof | |
| WO2021217722A1 (en) | Medium/low temperature supported nano copper oxide particle catalyst and preparation method therefor and application 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: 20240514 Address after: Room 301, Office Building, Shandong Bailiangchun Liquor Industry Co., Ltd., No. 9 Fushan Road, Fushan Village, Weigu Town, High tech Zone, Zibo City, Shandong Province, 255000 Patentee after: Zibo Xinhai Software Engineering Co.,Ltd. Country or region after: China Address before: 201799 South half of No. 500, 502 and 504 Xiuquan Road, Qingpu District, Shanghai Patentee before: Shanghai Jingshu Automobile Technology Service Center Country or region before: China |
|
| TR01 | Transfer of patent right |