CN115318303A - 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
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- CN115318303A CN115318303A CN202211027530.6A CN202211027530A CN115318303A CN 115318303 A CN115318303 A CN 115318303A CN 202211027530 A CN202211027530 A CN 202211027530A CN 115318303 A CN115318303 A CN 115318303A
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- Prior art keywords
- catalyst
- solution
- soot particles
- suspension
- diesel vehicle
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000002245 particle Substances 0.000 title claims abstract description 77
- 239000004071 soot Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000000779 smoke Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- 239000000243 solution Substances 0.000 claims description 64
- 238000003756 stirring Methods 0.000 claims description 56
- 239000007787 solid Substances 0.000 claims description 53
- 239000000725 suspension Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 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
- 238000001354 calcination Methods 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 150000000703 Cerium Chemical class 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-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
- 150000003839 salts Chemical class 0.000 claims description 8
- 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 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
- 238000000034 method Methods 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
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-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
- 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 3
- 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 3
- 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 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
- 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000002485 combustion reaction Methods 0.000 abstract description 12
- 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
- 239000002243 precursor Substances 0.000 abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- HQFBUALMHFGXCO-UHFFFAOYSA-N cerium oxocobalt Chemical compound [Ce].[Co]=O HQFBUALMHFGXCO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052709 silver Inorganic materials 0.000 abstract description 7
- 239000004332 silver Substances 0.000 abstract description 7
- 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 15
- 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 9
- 239000013078 crystal Substances 0.000 description 8
- 238000007084 catalytic combustion reaction Methods 0.000 description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 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 6
- 229910052757 nitrogen Inorganic materials 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
- 230000001105 regulatory effect Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- MNUSFSHFJMPRIV-UHFFFAOYSA-N [Co].[Ce] Chemical compound [Co].[Ce] MNUSFSHFJMPRIV-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000002131 composite material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011148 porous material Substances 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
- 230000008901 benefit Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000003915 air pollution 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
- 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
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 210000004072 lung Anatomy 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010453 quartz Substances 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
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 208000018569 Respiratory Tract disease Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000621 bronchi Anatomy 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
- 238000011161 development 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
- 238000011049 filling Methods 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
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing 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
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 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
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 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
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- 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
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- 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
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- 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 low temperature and a preparation method thereof. A structured cerium-cobalt oxide precursor is prepared through simple hydrothermal reaction, silver nitrate is impregnated in the precursor and then the precursor is calcined, silver species are successfully anchored on the surface of the structured cerium-cobalt oxide, and the catalyst for removing soot particles of a diesel vehicle at low temperature is successfully prepared. Based on the enhanced specific surface area, more active sites and the specific oxygen vacancy structure of the structured cerium cobalt oxide, the synergistic effect is generated with silver species on the surface, the reaction of the carbon smoke particles on the surface is enhanced, and the combustion temperature of the carbon smoke particles can be reduced to 325 ℃; the catalyst has high catalytic activity to soot particles under the condition of loose contact state with the soot 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, powerful engine horsepower, low carbon dioxide emission, wide application range and the like, is widely concerned under the current situation that crude oil is increasingly exhausted and the requirement for carbon dioxide emission is gradually strict, is one of the trend directions of the vehicle under the national energy-saving and emission-reduction control policy, but the emission of the diesel vehicle brings adverse effects on the control of the atmospheric environment and the physical health of residents in China. The pollutants in the exhaust gas discharged from diesel vehicles are very complex, including soot particles, carbon monoxide, hydrocarbons, nitrogen oxides, and the like. Wherein, the soot particles are pollutants which have the greatest harm and are most difficult to eliminate, and the particle size range of the soot particles is 0.05-1 μm. The carbon soot particles in the tail gas of the diesel vehicle are small in particle diameter, particularly small particles with the particle diameter smaller than 2.5 mu m are not easily blocked by nasal cavity villi, and can directly enter the bronchus after being inhaled into the lung, so that the gas exchange of the lung is influenced, and a series of respiratory tract and cardiovascular diseases are caused. Meanwhile, soot particles are also an important factor causing haze.
Currently, air pollution prevention and control work draws attention of many countries, and China also starts to focus on treating air pollution. In order to meet the increasingly strict regulatory requirements, there are three main methods for solving the problem of soot pollution discharged by diesel vehicles: firstly, the used fuel is improved or a novel environment-friendly alternative fuel is used; secondly, an engine of the diesel vehicle is improved; and thirdly, improving the exhaust aftertreatment system and additionally installing a tail gas purification system. The third method is generally considered to be most effective based on technical and economic considerations. In the actual exhaust gas after-treatment technology, the technology of combining a solid particle trap and a catalyst is the focus of current research, and the development of a catalyst with excellent performance is the core.
CN 107159231A discloses a preparation method of a single crystal supported catalyst for eliminating soot particles of a diesel vehicle at a low temperature, which is prepared by soaking a single crystal alpha-phase manganous oxide cube in a metal salt solution. 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 loading amount of the silver is 1% -20% of the mass of the carrier, the catalyst has good oxidation activity in the combustion of the soot particles, and the temperature of the soot particles during half of the combustion can be reduced from 642 ℃ to about 400 ℃ to reach the range of the operating temperature of a diesel engine. CN 106824161A discloses a preparation method of micron sheet-shaped carbon smoke combustion catalyst, which is prepared by mixing solution containing cerium source or lanthanum source with alkaline solution, precipitating at low temperature and calcining insoluble substances.
Catalysts common in the prior art for soot particle oxidation, such as: ceO (CeO) 2 The industrial application of the catalyst for oxidizing the soot particles is limited by the factors of the base compound, the perovskite type oxide, the noble metal based catalyst and the like, which are unfavorable for the contact of the active sites and the carbon particles due to the lack of a pore structure, high cost and easy poisoning of the noble metal, and low activity and easy loss of activity of the catalyst.
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 low temperature and a preparation method thereof. The catalyst has good effect on catalytic oxidation of soot particles under loose contact, can effectively convert the soot particles into carbon dioxide, and can remarkably reduce the temperature of thermal oxidation of the soot particles.
In order to achieve the aim, the invention provides a preparation method of a catalyst for removing soot particles of a diesel vehicle at low temperature, which comprises the following steps:
step 1: stirring soluble metal salt and ethanol water solution at the stirring speed of 300-500 r/min to form 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 for 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 performing ultrasonic treatment for 20-60 min at the ultrasonic power of 50-200W, the frequency of 20-130 kHz and the temperature of 20-40 ℃ to form a suspension a; adding silver nitrate into the suspension a stirred at the stirring speed of 300-500 r/min, reacting for 0.5-2 h to obtain suspension b, stopping stirring, transferring the suspension b to 90-120 ℃, 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; and crushing the calcined solid matter through a 300-500-mesh screen, and collecting powder below the screen, namely the catalyst for eliminating the carbon smoke 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 (II) nitrate hexahydrate, cobalt (II) acetate tetrahydrate and cobalt (II) chloride hexahydrate; the soluble cerium salt is one of cerium (III) nitrate hexahydrate and cerium (III) chloride heptahydrate.
The mass fraction of the ethanol water solution is 60-80%.
The alkaline aqueous solution is one of 1-3 mol/L aqueous ammonia solution, aqueous sodium hydroxide solution, aqueous sodium bicarbonate solution and aqueous sodium carbonate solution.
The catalytic oxidation performance of a single metal oxide catalyst on soot particulates is mainly affected by the redox capacity of the metal oxide, the mobility of the surface active species, and the contact with soot particulates. Under general conditions, the catalytic combustion performance of a single metal oxide catalyst on soot particles is not obviously improved, the soot particles can be effectively combusted only when the temperature is over 500 ℃, and the selectivity of forming carbon dioxide by catalytic combustion is not ideal. The composite metal oxide catalyst is a catalyst compounded by two or more than two metal elements, and the catalytic oxidation performance of the composite metal oxide catalyst on soot particles is mainly related by the self catalytic activity of the metal oxide and the synergistic catalytic action among different components. Many studies have shown that composite metal oxides benefit from single component metal oxide inter-crystalline phase changes, enhanced oxygen species storage in the structure, and synergy between components, which can significantly improve the catalytic combustion performance of the catalyst.
More preferably, the mass ratio of the soluble cobalt salt and 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; adding silver nitrate and solid powder in a mass ratio of (1.
The catalytic performance of a metal oxide depends to a large extent on its structure. In the hydrothermal or solvothermal preparation process of the metal oxide, the structure regulating substance in the precursor solution can prepare the metal oxide with various morphologies. Surfactants are the most commonly used structure-modifying substances. However, surfactants are difficult to remove and some surfactants of a particular function are expensive. The low molecular sugar can generate polymerization reaction to generate oligomer under the temperature and pressure of hydrothermal or solvent heat, and the oligomer has a structure regulation effect on metal ions in a liquid phase environment. Therefore, the 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 crystal nucleus growth rate and direction of a metal oxide precursor formed at an early stage, and can also play a role in regulating and controlling a metal oxidation structure.
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 soluble cobalt salt, soluble cerium salt, sugar and ethanol aqueous solution at the stirring speed of 300-500 r/min to form 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; 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 for 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 performing ultrasonic treatment for 20-60 min at the ultrasonic power of 50-200W, the frequency of 20-130 kHz and the temperature of 20-40 ℃ to form a suspension a; adding silver nitrate into a suspension a stirred at a stirring speed 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 substances, and calcining the solid substances at 400-600 ℃ for 2-5 h; and crushing the calcined solid matter through a 300-500-mesh screen, and collecting powder below the screen, namely the catalyst for eliminating the carbon smoke 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 to 50).
The soluble cobalt salt is one of cobalt (II) nitrate hexahydrate, cobalt (II) acetate tetrahydrate and cobalt (II) chloride hexahydrate, and the soluble cerium salt is one of cerium (III) nitrate hexahydrate and cerium (III) chloride heptahydrate.
The sugar is one or the combination of two or more of glucose, sucrose and lactose.
The mass fraction of the ethanol water solution is 60-80%.
The alkaline aqueous solution is one of 1-3 mol/L aqueous ammonia solution, aqueous sodium hydroxide solution, aqueous sodium bicarbonate solution and aqueous sodium carbonate solution.
The mass ratio of the nitrogenous substance to the soluble metal salt is (2-5): 1; the nitrogen-containing substance is one or a combination of two or more of hexamethylenetetramine, urea, glycine, ethylenediamine, hexamethyldisilazane and tetramethyldivinyldisilazane.
Preferably, the mass ratio of the solid powder to the water in the step 2 is (0.02-0.05): 1; adding silver nitrate and solid powder in a mass ratio of (1.
The invention has the beneficial effects that:
(1) The invention prepares the precursor of the structured cerium cobalt oxide through simple hydrothermal reaction, impregnates the precursor of the structured cerium cobalt oxide with silver nitrate and then calcines the precursor of the structured cerium cobalt oxide, successfully anchors silver species on the surface of the structured cerium cobalt oxide, successfully prepares the catalyst for removing carbon smoke 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 amplification 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 the structured cerium dioxide, the cobaltosic oxide and the silver, the catalyst prepared by the invention has high catalytic activity on soot particles under the condition of loose contact state with the soot particles and no existence of nitrogen oxide; and can reduce the combustion temperature of the soot particles to 325 ℃.
Drawings
FIG. 1 is a scanning electron microscope image of a catalyst prepared by the invention for removing soot particles of a diesel vehicle at low temperature, (A) example 3, (B) example 4, (C) example 5, and (D) example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments further describe the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1 preparation method of soot particle catalyst
(1) Dissolving 3.5g of cobalt nitrate hexahydrate in 100g of 70% ethanol aqueous solution at a stirring speed of 300r/min to form a solution I; adjusting the pH value of the solution I to 9.5 by using 2mol/L ammonia water solution, and continuously stirring for 1h at the stirring speed of 300r/min to form a solution II; transferring the solution II to a polytetrafluoroethylene inner container, putting the solution II into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reacting for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water for three times respectively, and drying in a constant-temperature oven at 80 ℃ 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 performing 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 the stirring speed of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker filled with the suspension b to a constant-temperature oven, drying at 120 ℃ for 12h, evaporating the water content of the suspension b, collecting the residual solid matter, and calcining the solid matter in a muffle furnace at 550 ℃ for 2h; the calcined solid matter was pulverized and sieved through a 300 mesh sieve, and the powder under the sieve was collected to obtain silver-doped cobaltosic oxide, which was the catalyst prepared in this example.
Example 2 preparation method of soot particle catalyst
(1) Dissolving 3.5g of cerous nitrate hexahydrate in 100g of 70% ethanol aqueous solution at the stirring speed 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 at the stirring speed of 300r/min for 1h to form a solution II; transferring the solution II to a polytetrafluoroethylene inner container, putting the solution II into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reacting for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water for three times respectively, and drying in a constant-temperature oven at 80 ℃ 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 performing 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 the stirring speed of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker filled with the suspension b to a constant-temperature oven, drying at 120 ℃ for 12h, evaporating the water content of the suspension b, collecting the residual solid matter, and calcining the solid matter in a muffle furnace at 550 ℃ for 2h; the calcined solid material was pulverized and sieved through a 300-mesh sieve, and the powder under the sieve was collected to obtain silver-doped ceria, which was the catalyst prepared in this example.
Example 3 preparation method of soot particle catalyst
(1) Dissolving 2.8g of cerous nitrate hexahydrate and 0.7g of cobalt nitrate hexahydrate in 100g of 70% ethanol aqueous solution at a stirring speed 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 at the stirring speed of 300r/min for 1h to form a solution II; transferring the solution II to a polytetrafluoroethylene inner container, putting the solution II into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reacting for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water for three times respectively, and drying in a constant-temperature oven at 80 ℃ 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 performing 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 the stirring speed of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker filled with the suspension b to a constant-temperature oven, drying at 120 ℃ for 12h, evaporating the water content of the suspension b, collecting the residual solid matter, and calcining the solid matter in a muffle furnace at 550 ℃ for 2h; the calcined solid material was pulverized and sieved through a 300-mesh sieve, and the powder under the sieve was collected to obtain the silver-doped cobalt-cerium bimetallic oxide, which was the catalyst prepared in this example.
Example 4 preparation method of soot particle catalyst
(1) Dissolving 2.8g of cerous nitrate hexahydrate, 0.7g of cobalt nitrate hexahydrate and 1g of glucose in 100g of ethanol aqueous solution with the mass fraction of 70% at the stirring speed 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 at the stirring speed of 300r/min for 1h to form a solution II; transferring the solution II to a polytetrafluoroethylene inner container, filling the solution II into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reacting for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water for three times respectively, and drying in a constant-temperature oven at 80 ℃ 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 performing 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 the stirring speed of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker filled with the suspension b to a constant-temperature oven, drying at 120 ℃ for 12h, evaporating the water content of the suspension b, collecting the residual solid matter, and calcining the solid matter in a muffle furnace at 550 ℃ for 2h; the calcined solid material was pulverized and sieved through a 300-mesh sieve, and the powder under the sieve was collected to obtain the flaky silver-doped cobalt-cerium bimetallic oxide, which was the catalyst prepared in this example.
Example 5 preparation method of soot particle catalyst
(1) Dissolving 2.8g of cerous nitrate hexahydrate and 0.7g of cobalt nitrate hexahydrate in 100g of 70% ethanol aqueous solution at a stirring speed 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, adding 8g of tetramethyl divinyl disilazane, and continuously stirring at the stirring speed of 300r/min for 1h to form a solution II; transferring the solution II to a polytetrafluoroethylene inner container, putting the solution II into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reacting for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water for three times respectively, and drying in a constant-temperature oven at 80 ℃ 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 performing 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 the stirring speed of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker filled with the suspension b to a constant-temperature oven, drying at 120 ℃ for 12h, evaporating the water content of the suspension b, collecting the residual solid matter, and calcining the solid matter in a muffle furnace at 550 ℃ for 2h; the calcined solid material was pulverized and sieved through a 300-mesh sieve, and the powder under the sieve was collected to obtain the flaky silver-doped cobalt-cerium bimetallic oxide, which was the catalyst prepared in this example.
Example 6 preparation method of soot particle catalyst
(1) Dissolving 2.8g of cerous nitrate hexahydrate, 0.7g of cobalt nitrate hexahydrate and 1g of glucose in 100g of ethanol aqueous solution with the mass fraction of 70% at the stirring speed 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, adding 8g of tetramethyl divinyl disilazane, and continuously stirring at the stirring speed of 300r/min for 1h to form a solution II; transferring the solution II to a polytetrafluoroethylene inner container, putting the solution II into a stainless steel reaction kettle, placing the reaction kettle at 180 ℃ for reacting for 8 hours, naturally cooling to 25 ℃, filtering insoluble substances, washing with ethanol and water for three times respectively, and drying in a constant-temperature oven at 80 ℃ 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 performing 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 the stirring speed of 300r/min, stirring and reacting for 1h to obtain a suspension b, stopping stirring, transferring a beaker filled with the suspension b to a constant-temperature oven, drying at 120 ℃ for 12h, evaporating the water content of the suspension b, collecting the residual solid matter, and calcining the solid matter in a muffle furnace at 550 ℃ for 2h; the calcined solid matter is crushed and then screened by a 300-mesh screen, and the powder under the screen is collected to obtain the silver-doped cobalt-cerium bimetallic oxide with a three-dimensional interconnected porous structure, namely the catalyst prepared in the embodiment.
Test example 1 morphology of the catalyst
The catalysts prepared in examples 3, 4, 5 and 6 were characterized by scanning electron microscopy, and the results are shown in FIG. 1.
Specific surface area and pore structure tests were performed on the catalysts prepared in example 3, example 4, example 5, and example 6. The specific surface area is calculated by using a Brunauer-Emmett-Teller (BET) model, and the pore diameter (D) is calculated by using a Barren-Joyner-Halenda (BJH) model p ) And (4) distribution. The results are shown in Table 1.
TABLE 1 specific surface area test results
| 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 |
From FIG. 1, it can be seen that example 3, in which glucose and tetramethyldivinyldisilazane were not added, exhibited a block shape; example 4, prepared with the addition of glucose, and example 5, prepared with the addition of tetramethyldivinyldisilazane, exhibited a distinct lamellar structure. This is because under hydrothermal conditions, the coordination attraction between the oligomers formed by glucose polymerization and tetramethyldivinyldisilazane has a mediating effect on the metal oxide precursor, causing it to nucleate growth in the planar direction. In addition, example 6, prepared with the addition of glucose and tetramethyldivinyldisilazane, exhibits a distinct three-dimensional interconnected porous structure with distinct macropores (> 50 nm) present. This indicates that glucose and tetramethyldivinyldisilazane have a synergistic regulating effect on the structure of the composite metal oxide. Probably because the polymerization of glucose into oligomers at high temperature has an adjusting effect on the structure of the metal oxide precursor, the metal oxide precursor crystal nucleus can be polymerized into a sheet shape and continuously grows, and the sheet-shaped metal oxide precursor is formed after the hydrothermal reaction is finished; the addition of the tetramethyl divinyl disilazane enables metal oxide precursor crystal nuclei to rapidly grow along with the layered structure of alcohol and metal ion coordination, as the reaction proceeds, the sheet structure further grows and self-assembles and polymerizes to form the three-dimensional porous structured metal oxide precursor, and the structured metal oxide catalyst with the silver-doped three-dimensional porous structure is prepared through final calcination treatment.
The specific surface area test is consistent with the test result of a scanning electron microscope, and the specific surface area and the pore size distribution of the catalyst are improved by adding glucose and tetramethyl divinyl disilazane. Example 6 a unique three-dimensional interconnected porous structure that 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 used for temperature programming, oxygen, nitric oxide, water vapor and nitrogen are continuously introduced into a reactor, and the gas at the outlet is tested by a Fourier infrared spectrum gas tester.
5mg of soot particles and 50mg of catalyst are mixed to form loose contact, and a mixed sample is diluted by 100mg of inert silica and then is put into a quartz tube with the inner diameter of 10 mm; the quartz tube is placed in a reactor for temperature programmed oxidation, and temperature programmed heating and reaction temperature control are carried out through a tubular electric heating furnace in the reactor. The temperature range of the temperature programming experiment is 50-650 ℃, the temperature rising rate is 2.5 ℃/min, and the temperature is maintained for 30min after the target temperature is reached. The catalytic tests of 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 soot particles is monitored using online mass spectrometry, 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 judged by the following formula:
in the formula
And C CO The concentration of carbon dioxide and the concentration of carbon monoxide at 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: selectivity to carbon dioxide; the reaction temperatures at which the soot particle conversion is 10%, 50% and 90%, respectively, are denoted by 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 Performance results for catalysts under a balance of gas atmosphere of 10% oxygen, 10% water vapor and nitrogen
From the results of examples 1-3, it can be seen that the soot catalytic combustion performance of the silver-doped ceria catalyst is better than that of the silver-doped tricobalt tetroxide catalyst, and the selectivity of the two catalysts for the oxidation combustion of soot particles into carbon dioxide is not ideal; 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 soot oxidation combustion is also obviously reduced. This is probably because cobalt successfully incorporates 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 reactive sites.
From the test results of examples 3-6, it can be seen that the addition of glucose and tetramethyldivinyldisilazane during the preparation process improves the catalyst performance and lowers the temperature required for soot particle combustion. The reason for this is probably that the polymerization of glucose into oligomers at high temperature has an effect of regulating the structure of the metal oxide precursor, and can polymerize metal oxide precursor crystal nuclei into sheets 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 metal oxide precursor crystal nuclei to rapidly grow along with the layered structure of alcohol and metal ion coordination, as the reaction proceeds, the sheet structure further grows and self-assembles and polymerizes to form the three-dimensional porous structured metal oxide precursor, and the structured metal oxide catalyst with the silver-doped three-dimensional porous structure is prepared through final calcination treatment. Such a three-dimensional porous structure facilitates the adsorption of soot particles on the catalyst surface and further promotes the catalytic reaction.
To further approximate the actual use environment, the catalyst prepared in the examples of the present invention was subjected to catalytic tests under conditions of 1000ppm of nitric oxide, 10% of water vapor, 10% of oxygen and nitrogen balance gas, and a total gas flow rate 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 because part of the nitric oxide is oxidized by the catalyst to nitrogen dioxide, which is more catalytically active than oxygen, enhancing the oxidation of soot particles. These results also show that example 6 of the present invention has a very good catalytic performance for simulating the oxidative combustion of soot particles in diesel exhaust, and can effectively convert soot particles into carbon dioxide at about 400 ℃.
TABLE 2 Performance results of the catalyst under a balance atmosphere of 1000ppm nitric oxide, 10% water vapor, 10% oxygen, and nitrogen
Claims (10)
1. The preparation method of the catalyst for removing soot particles of the diesel vehicle at low temperature is characterized by comprising the following steps of:
step 1: stirring soluble metal salt and ethanol water solution at the stirring speed of 300-500 r/min to form 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 for three times respectively, and drying at 80-120 ℃ for 6-12 h to obtain solid powder.
And 2, step: dispersing the solid powder obtained in the step (1) in water, and performing ultrasonic treatment for 20-60 min at the ultrasonic power of 50-200W, the frequency of 20-130 kHz and the temperature of 20-40 ℃ to form a suspension a; adding silver nitrate into a suspension a stirred at a stirring speed 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 ℃, keeping for 12-18 h, evaporating the water of the suspension b, collecting solid substances, and calcining the solid substances at 400-600 ℃ for 2-5 h; crushing the calcined solid matter through a 300-500 mesh screen, and collecting powder below the screen, namely the catalyst for eliminating the carbon smoke particles of the diesel vehicle;
the soluble metal salt is one of soluble cobalt salt or soluble cerium salt.
2. The preparation method of the catalyst for removing soot particles of the diesel vehicle at low temperature is characterized by comprising the following steps of:
step 1: stirring soluble cobalt salt, soluble cerium salt, sugar and ethanol aqueous solution at the stirring speed of 300-500 r/min to form 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 for 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 performing ultrasonic treatment for 20-60 min at the ultrasonic power of 50-200W, the frequency of 20-130 kHz and the temperature of 20-40 ℃ to form a suspension a; adding silver nitrate into the suspension a stirred at the stirring speed of 300-500 r/min, reacting for 0.5-2 h to obtain suspension b, stopping stirring, keeping the suspension b at the temperature of 90-120 ℃ for 12-18 h, evaporating the water of the suspension b, collecting solid matters, and calcining the solid matters at the temperature of 400-600 ℃ for 2-5 h; and crushing the calcined solid matter through a 300-500-mesh screen, and collecting powder below the screen, namely the catalyst for removing the carbon smoke particles of the diesel vehicle at low temperature.
3. The method for preparing the catalyst for removing soot particles of the diesel vehicle at low temperature as claimed in claim 1 or 2, wherein the soluble cobalt salt is one of cobalt (II) nitrate hexahydrate, cobalt (II) acetate tetrahydrate and cobalt (II) chloride hexahydrate; the soluble cerium salt is one of cerium (III) nitrate hexahydrate and cerium (III) chloride heptahydrate.
4. The preparation method of the catalyst for removing soot particles of the diesel vehicle at low temperature as claimed in claim 1 or 2, wherein the mass fraction of the ethanol aqueous solution is 60-80%.
5. The method for preparing the catalyst for removing soot particles of the diesel vehicle at low temperature according to claim 1 or 2, wherein 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.
6. The preparation method of the catalyst for removing soot particles of the diesel vehicle at low temperature as claimed in 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).
7. The method for preparing the catalyst for removing soot particles of the diesel vehicle at low temperature according to claim 2, wherein the sugar is one or a combination of two or more of glucose, sucrose and lactose.
8. The preparation method of the catalyst for removing soot particles of the diesel vehicle at low temperature according to claim 2, wherein the mass ratio of the nitrogen-containing substance to the soluble metal salt is (2-5): 1; the nitrogen-containing substance is one or a combination of two or more of hexamethylenetetramine, urea, glycine, ethylenediamine, hexamethyldisilazane and tetramethyldivinyldisilazane.
9. The preparation method of the catalyst for removing soot particles of the diesel vehicle at low temperature according to claim 2, wherein the mass ratio of the solid powder to the water in the step 2 is (0.02-0.05): 1; adding silver nitrate and solid powder in a mass ratio of (1.
10. The catalyst for removing soot particles of a diesel vehicle at low temperature is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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