CN116832856A - Sulfur capture catalyst for diesel engine and preparation method thereof - Google Patents
Sulfur capture catalyst for diesel engine and preparation method thereof Download PDFInfo
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- CN116832856A CN116832856A CN202310837761.1A CN202310837761A CN116832856A CN 116832856 A CN116832856 A CN 116832856A CN 202310837761 A CN202310837761 A CN 202310837761A CN 116832856 A CN116832856 A CN 116832856A
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- catalyst
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- diesel engine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 82
- 239000011593 sulfur Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- -1 alkali metal salts Chemical class 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 38
- 239000000919 ceramic Substances 0.000 claims description 24
- 239000002808 molecular sieve Substances 0.000 claims description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000007580 dry-mixing Methods 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 7
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052815 sulfur oxide Inorganic materials 0.000 abstract description 5
- 238000011144 upstream manufacturing Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 231100000572 poisoning Toxicity 0.000 description 9
- 230000000607 poisoning effect Effects 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7053—A-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/087—X-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7607—A-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The preparation method of the sulfur trapping catalyst for the diesel engine comprises the following steps of: modified alumina: alkali metal salts: transition metal salts: extrusion aid: pore-forming agent: inorganic strong acid peptizing agent: h2o=33-40%: 8-13%:3-5%:1.5-3%:2-4.5%:0.5-1%:2-6%: and (3) uniformly mixing 27.5-50% by mass percent to obtain catalyst pug, extruding the catalyst pug to form, drying and calcining to obtain the sulfur trapping catalyst. The sulfur trapping catalyst prepared by the invention is arranged at the upstream of the post-treatment catalyst, can endure the application scene of high humidity and heat of a diesel engine, and can efficiently trap SO in the whole vehicle operation 2 And sulfate, effectively prevent sulfur oxides from polluting the post-treatment catalyst under different application scenes.
Description
Technical Field
The invention belongs to the technical field of diesel engine post-treatment catalysts, and particularly relates to a sulfur trapping catalyst for a diesel engine and a preparation method thereof.
Background
The diesel engine has high fuel economy, good dynamic property and wide power range coverage, is a main power source in the fields of commercial vehicles, engineering machinery, power generation equipment, ships, national defense equipment and the like, and is an important product in the equipment manufacturing industry in China. In order to meet the requirements of increasingly stringent emission regulations, diesel engine tail gas is cooperatively purified through a post-treatment catalyst, so that the aim of pollutant emission reduction is fulfilled. The diesel engine post-treatment catalyst adopts the technical route of oxidation catalyst (DOC) +particle catcher (cDPF) +selective catalytic reduction (SCR) +ammonia leakage catalyst (ASC) to meet the requirements of low temperature, high efficiency, high durability and full working condition coverage in the six stages of China. In order to ensure the efficient operation of the post-treatment catalyst, the state six-law requires that the sulfur content of diesel oil is required to be lower than 10ppm, and the sulfur content in tail gas after in-cylinder combustion is 1-2 ppm, but even under the condition of low sulfur content, long-term accumulation tends to cause the occurrence of catalyst poisoning. The use of non-compliant diesel fuel, affected by regional differences, exacerbates the catalyst poisoning phenomenon, and the failure caused by sulfur poisoning is common. In the future, aiming at the ultra-low emission requirements of China seven, catalysts such as close-coupled SCR (CC-SCR), selective catalytic reduction trap (SDPF) and the like are likely to be used for purifying the tail gas of the diesel engine in a large amount, but with the forward shift of the position of the SCR catalyst, the problem of sulfur poisoning is more prominent.
The catalyst for the national sixth post-treatment of the diesel engine mostly adopts metals such as Pt, pd, cu and the like as active species, and achieves the aim of purifying pollutants through efficient synergistic catalysis. However, the above-mentioned several active metals are poor in sulfur resistance and in SO 2 Is easily oxidized to PtSO under the atmosphere 4 、PdSO 4 、CuSO 4 And sulfate, causing irreversible deactivation of the catalyst. In addition, due to the influence of oxygen enrichment and damp heat application conditions of the diesel engine, sulfides easily corrode parts such as a post-treatment stainless steel shell, an engine cylinder cover and the like to generate FeSO 4 、ZnSO 4 、CaSO 4 And compounding sulfated ash.
In order to prevent sulfur poisoning, one idea is to improve the sulfur poisoning resistance of the catalyst by improving the catalyst formula. Patent CN115555039a proposes to use Cu, zn, mn, ni instead of noble metal active species (Pt, pd) as active component of cDPF to reduce the occurrence of sulfur poisoning of cDPF catalyst. Patent CN114534776a proposes that DOC adopts zone coating mode, and the sulfur resistance of DOC catalyst is improved by dispersing Pt and three non-noble metal active components (Ti, W, mo, ce) in the front zone and dispersing the fourth active components (Cu, fe, zn) in the rear zone. The patent adopts a method of partially replacing noble metal active species by introducing non-noble metal elements and rare earth elements, so that the sulfur resistance of the catalyst is improved to a certain extent, but the non-noble metal catalyst has poor oxidation-reduction activity and thermal stability, and is easy to cause tail emission exceeding. Another idea is to reduce the occurrence of post-treatment catalyst poisoning by catalyst combination and overall control strategy optimization. Patent CN1234473a proposes a method for optimizing the gasoline engine calibration strategy, which adopts a combination method of sulfur trapping catalyst and NOx storage catalyst, and achieves NO by controlling the air-fuel ratiox and sulfur oxide storage and release cycle requirements, the sulfur trapping catalyst is an oxide doped with alkaline earth metals and rare earth elements in Mg/Al. Patent CN111255551a proposes a high power diesel pollutant discharge reverse flow catalytic conversion device with sulfur trap, integrated sulfur trap and particulate filter, wherein the sulfur trap catalyst comprises a through silicon carbide carrier and Pt/Ag-SiO coated thereon 2 And (3) a catalyst. The above patent provides a reference idea for solving the sulfur poisoning of the catalyst, but is not mentioned for the sulfur trap catalyst preparation method, the trapping efficiency, the catalyst sulfur capacity and the regeneration scheme.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a sulfur trapping catalyst for a diesel engine and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the sulfur trapping catalyst for the diesel engine comprises the following steps of: modified alumina: alkali metal salts: transition metal salts: extrusion aid: pore-forming agent: inorganic strong acid peptizing agent: h 2 O=33-40%: 8-13%:3-5%:1.5-3%:2-4.5%:0.5-1%:2-6%: and (3) uniformly mixing 27.5-50% by mass percent to obtain catalyst pug, extruding the catalyst pug to form, drying and calcining to obtain the sulfur trapping catalyst.
Further, the molecular sieve is a powder material, including but not limited to one or a combination of two of OFF, 4A, 5A, 13X.
Further, the molecular sieve is one or two of Ca type, K type, na type and Na/K type; the molar ratio of silicon dioxide to aluminum oxide in the molecular sieve is less than or equal to 10:1, wherein Ca, K, na, na/K cations are coordinated with framework Al, and the molar ratio of alkali metal elements to Al elements is less than or equal to 0.85:1.
Further, the modified alumina has a boehmite crystal structure, the grain size is less than or equal to 1 mu m, the alumina content is more than or equal to 95%, and NO 3 - The content is less than or equal to 5 percent.
Further, the alkali metal salt is nitrate obtained by adding alkali metal elements into nitric acid, and the purity of the nitrate is more than or equal to 95%; the alkali metal element is one or two of Ca, mg and Ba.
Further, the transition metal salt is nitrate obtained by adding transition metal elements into nitric acid, and the purity of the nitrate is more than or equal to 95%; the transition metal element is one or two of Fe, co, ce, ni.
Further, the extrusion aid is one or a combination of more than two of hydrophilic carboxymethyl cellulose, starch, glycerol and hydroxyethyl cellulose, and the viscosity of the extrusion aid is 1500-3000 mPa.s.
Further, the pore-forming agent is one or a combination of more than two of polyethylene glycol, carbon powder and polyvinyl alcohol, and the polymerization degree of the pore-forming agent is 4000-6000.
Further, the inorganic strong acid peptizing agent is one or a mixture of two of concentrated nitric acid and concentrated hydrochloric acid.
The preparation method of the sulfur trapping catalyst for the diesel engine comprises the following specific steps:
(1) Adding molecular sieve, modified alumina, alkali metal salt, transition metal salt and extrusion aid into a mixer, and continuously dry-mixing for 0.5-1h until uniformity;
(2) Adding an inorganic strong acid peptizing agent and H into the dry blend prepared in the step (1) 2 O, wet mixing for 0.5-1h;
(3) After the wet mixing in the step (2) is completed, adding a pore-forming agent, continuing the wet mixing for 1-1.5h to obtain pug, putting the pug into a vacuumizing pug mill, and vacuumizing and mixing for 3-5 times;
(4) Putting the pug which is well treated in the step (3) into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, and cutting according to the required height to obtain a catalyst wet material;
(5) Drying the wet catalyst material prepared in the step (4) at a low temperature of 35-50 ℃ by microwaves to obtain an integral honeycomb ceramic catalyst;
(6) Asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials;
(7) And (3) calcining the integral honeycomb ceramic catalyst subjected to hole blocking at a high temperature, and calcining at 550-650 ℃ for 3-5 hours to obtain the wall-flow type integrated extrusion molding sulfur trapping catalyst.
Compared with the prior art, the method has at least the following advantages:
(1) The high-trapping type wall-flow catalyst is prepared and is arranged at the upstream of the post-treatment catalyst, and the gas/solid sulfide trapping can be satisfied by the application of the ultra-high specific surface area alkaline trapping material, so that the pollution of the downstream post-treatment catalyst by sulfur is avoided.
(2) The sulfide is trapped by coupling Ca-type, K-type, na/K-type OFF, 4A, 5A and 13X molecular sieve catalysts and adding and kneading basic oxides according to a specific proportion, so that the sulfide is in a reaction path of reaction, anchoring and trapping. In addition, aiming at the ultra-low silicon-aluminum ratio molecular sieve, the doping effect of Ce, fe, co, ni or bimetal is fully utilized by adding transition metal elements, the positive charge of Al atoms of a molecular sieve framework is increased, the electrostatic potential of Al-O is promoted to be smaller, the acting force between Al and O atoms of an adjacent framework is improved, a stable Me (OH) 2+ -molecular sieve framework coordination structure is formed, the framework Al stability is effectively improved, the framework dealumination is inhibited, and the high-temperature stability of the catalyst is improved.
(3) The high sulfide trapping type wall flow catalyst adopts a molecular sieve porous effect to achieve the maximum SO2 trapping, and meanwhile, because the gas outlet end adopts a semi-plugging mode, the sulfated ash forms a terminal trapping effect in the catalyst. Through high-temperature calcination and high-pressure air gun blowing, the effects of sulfide desorption and sulfated ash removal can be met, and the aim of recycling is fulfilled.
Drawings
FIG. 1 is a schematic diagram of the sulfur trap catalyst trapping principle;
FIG. 2 is an XRD spectrum of a sulfur trap catalyst of example 1 of the present invention;
fig. 3 is a graph comparing sulfur capacities and corresponding NOx conversion efficiencies of sulfur trap catalysts of examples 1 to 5 and comparative example 1 of the present invention.
Detailed Description
The invention will be further elucidated with reference to the drawings and the embodiments.
A preparation method of a sulfur trapping catalyst for a diesel engine, wherein the sulfur trapping catalyst is arranged at the upstream of a post-treatment catalyst and is a wall flow type integrated extrusion molding catalyst prepared by wall flow type honeycomb ceramic carrier extrusion molding equipment. The wall flow honeycomb ceramic carrier extrusion molding equipment is equipment in the prior art.
The preparation method of the sulfur trapping catalyst for the diesel engine comprises the following steps of: modified alumina: alkali metal salts: transition metal salts: extrusion aid: pore-forming agent: inorganic strong acid peptizing agent: h2o=33-40%: 8-13%:3-5%:1.5-3%:2-4.5%:0.5-1%:2-6%: and (3) uniformly mixing 27.5-50% by mass percent to prepare catalyst pug, extruding the catalyst pug to form, drying and calcining to obtain the sulfur trapping catalyst. The specific preparation method comprises the following steps:
(1) Adding molecular sieve, modified alumina, alkali metal salt, transition metal salt and extrusion aid into a mixer, and continuously dry-mixing for 0.5-1h until uniformity;
(2) Adding an inorganic strong acid peptizing agent and H2O into the dry blend prepared in the step (1), and wet mixing for 0.5-1H;
(3) After the wet mixing in the step (2) is completed, adding a pore-forming agent, continuing the wet mixing for 1-1.5h to obtain pug, putting the pug into a vacuumizing pug mill, and vacuumizing and mixing for 3-5 times;
(4) Putting the pug which is well treated in the step (3) into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, and cutting according to the required height to obtain a catalyst wet material;
(5) Drying the wet catalyst material prepared in the step (4) at a low temperature of 35-50 ℃ by microwaves to obtain an integral honeycomb ceramic catalyst;
(6) And (3) asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials. The asymmetric hole blocking refers to that if the air inlet end blocks the hole, the corresponding air outlet end does not block the hole; if the air inlet end is not plugged, the corresponding air outlet end is plugged. The holes are not straight in and straight out, so that particles, ash and sulfate ash can be trapped and are not discharged into the air;
(7) And (3) calcining the integral honeycomb ceramic catalyst subjected to hole blocking at a high temperature, and calcining at 550-650 ℃ for 3-5 hours to obtain the wall-flow type integrated extrusion molding sulfur trapping catalyst.
In the above method, the molecular sieve is a powder material, including but not limited to one or two of OFF, 4A, 5A, and 13X, which are all common materials in industry and commercially available. The molecular sieve is one or two of Ca type, K type, na type and Na/K type; the mole ratio of silicon dioxide to aluminum oxide in the molecular sieve, namely the silicon-aluminum mole ratio is less than or equal to 10:1, wherein Ca, K, na, na/K element is coordinated with framework Al in a hydroxyl form, and the mole ratio of alkali metal element to Al element is less than or equal to 0.85:1.
The hydrated alumina has a boehmite crystal structure, the grain size is less than or equal to 1 mu m, the alumina content is more than or equal to 95%, and the NO 3-content is less than or equal to 5%.
The alkali metal salt is nitrate obtained by adding alkali metal elements into nitric acid, and the purity of the nitrate is more than or equal to 95%; the alkali metal element is one or two of Ca, mg and Ba.
The transition metal salt is nitrate obtained by adding transition metal elements into nitric acid, and the purity of the nitrate is more than or equal to 95%; the transition metal element is one or two of Fe, co, ce, ni.
The extrusion aid is one or a combination of more than two of hydrophilic carboxymethyl cellulose, starch, glycerol and hydroxyethyl cellulose, and the materials are all commercially available. The viscosity of the extrusion aid is 1500-3000 mPa.s.
The pore-forming agent is one or a combination of more than two of polyethylene glycol, carbon powder and polyvinyl alcohol, and the materials are all commercially available. The polymerization degree of the pore-forming agent is 4000-6000.
The inorganic strong acid peptizing agent is one or a mixture of two of concentrated nitric acid and concentrated hydrochloric acid.
Fig. 1 shows the sulfur trap catalyst trapping principle. As shown in fig. 1, the air inlet end face and the air outlet end face of the extruded honeycomb ceramic catalyst 4 are subjected to asymmetric pore blocking by using a pore blocking material 3. After passing through the porous sulfur trapping catalyst, the sulfur-containing gas (SO 2/SO3 gas) 2 undergoes oxidation-reduction reaction with cations such as Na, K, ca and the like in the catalyst, and sulfate species 5 are generated in the honeycomb holes of the catalyst. In addition, the sulfate substance 1 in the sulfur-containing gas cannot pass through the plug 3 or pass through the sulfur-trapping catalyst and be trapped in the monolithic ceramic honeycomb catalyst 4 after passing through the sulfur-trapping catalyst. The sulfide proceeds along the reaction path 6 of reaction, anchoring, and trapping, and is trapped, and the sulfur-free tail gas 7 is discharged.
The sulfur trapping catalyst can endure the application scene of high humidity and heat of a diesel engine, can efficiently trap SO2 and sulfate in the whole vehicle operation, has a sulfur capacity of 180-300g/cat, and effectively prevents sulfur oxides from polluting the post-treatment catalyst in different application scenes. After the sulfur capturing catalyst reaches the maximum sulfur capacity, the catalyst can be disassembled for regeneration at the high temperature of 450-700 ℃ for 1-1.5h, and the portable air compressor of 450-600kPa is adopted for ash removal of sulfated ash, so that the catalyst can be reused.
The mixer, the vacuumizing pug mill, the high-pressure vacuum extruder, the drying and calcining kiln equipment and the like used in the method are all equipment in the prior art.
Example 1
To the mixer according to NaK/OFF (molar ratio of silicon to aluminum=7): modified alumina (wt% ai 2 o3=95%, wt% NO3- =5%): ba (NO 3) 2: ce (NO 3) 3: hydroxyethyl cellulose = 33%:10%:5%:2.5%:2.5% of the total weight of the mixture is added, and dry mixing is continued until the mixture is uniform. To the dry mix was added concentrated nitric acid solution (concentration 63%): h2o=2%: the 44.5% portion was added to the mixer uniformly and slowly and wet mixed for 1h. After the wet materials are uniformly mixed, 0.5 percent polyethylene glycol (polymerization degree 6000) is added, after the wet mixing is continued for 1.5 hours, the pug is put into a vacuumizing pugging machine for pugging, and vacuumizing and pugging are carried out for 3 times. Putting the well-kneaded pug into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, cutting the blank into a required height to obtain a catalyst wet material, and drying the catalyst wet material at a low temperature of 35 ℃ for 8 hours by microwave drying to obtain the integral honeycomb ceramic catalyst. And (3) asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials, and calcining for 3 hours at 650 ℃ to prepare the wall-flow type integrated extrusion molding sulfur trapping catalyst, which is marked as 'sample 1'.
Example 2
Into the mixer as Na/4A (molar ratio of silicon to aluminum=2): modified alumina (wt% ai 2 o3=96%, wt% NO3- =4%): mg (NO 3) 2: ce (NO 3) 4: carboxymethyl cellulose = 38%:8%:3%:1.0%: 2% and dry-blending continuously until uniform. To the dry mix was added as a hydrochloric acid solution (38%): h2o=3%: the 44% portion was added to the mixer uniformly and slowly and wet mixed for 0.5h. After the wet materials are uniformly mixed, 1% polyvinyl alcohol (with a polymerization degree of 3000) is added, and after the wet mixing is continued for 0.5h, the pug is put into a vacuumizing pugging machine for pugging, and vacuumizing and pugging are carried out for 5 times. Putting the well-kneaded pug into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, cutting the blank into a required height to obtain a catalyst wet material, and drying the catalyst wet material at a low temperature of 50 ℃ for 5 hours by microwaves to obtain the integral honeycomb ceramic catalyst. And (3) asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials, and calcining for 5 hours at 550 ℃ to prepare the wall-flow type integrated extrusion formed sulfur trapping catalyst, which is marked as 'sample 2'.
Example 3
Into the mixer as Na/Ca-13X (molar ratio of silicon to aluminum=5): modified alumina (wt% ai 2 o3=97.5%, wt% NO3- =2.5%): ca (NO 3) 2: fe (NO 3) 4: starch=34%: 9%:3.75%:2.5%: the proportion of 1% is continuously dry-mixed until uniform. To the dry mix was added concentrated hydrochloric acid solution (36%): h2o=2%: the 47% ratio was added to the mixer uniformly and slowly and wet mixed for 0.5h. After the wet materials are uniformly mixed, 0.75% polyethylene glycol (polymerization degree 3000) is added, and after the wet mixing is continued for 0.5h, the pug is put into a vacuumizing pugging machine for pugging, and vacuumizing and pugging are carried out for 4 times. Putting the well-kneaded pug into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, cutting the blank into a required height to obtain a catalyst wet material, and drying the catalyst wet material at a low temperature of 60 ℃ for 6 hours by microwaves to obtain the integral honeycomb ceramic catalyst. And (3) asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials, and calcining for 4 hours at 550 ℃ to prepare the wall-flow type integrated extrusion formed sulfur trapping catalyst, which is marked as 'sample 3'.
Example 4
Into the mixer according to Ca/5A (molar ratio of silicon to aluminum=3): modified alumina (wt% ai 2 o3=99%, wt% NO3- =1%): ca (NO 3) 2: co (NO 3) 4: sesbania powder = 36%:10%:3%:2%:2% and dry-blending continuously until uniform. To the dry mix was added concentrated nitric acid solution (concentration 63%): h2o=2%: the 44.75% portion was added to the mixer uniformly and slowly and wet mixed for 0.5h. After the wet materials are uniformly mixed, 0.25% polyvinyl alcohol (polymerization degree 4000) is added, after the wet mixing is continued for 2 hours, the pug is put into a vacuumizing pugging machine for pugging, and vacuumizing and pugging are carried out for 4 times. Putting the well-kneaded pug into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, cutting the blank into a required height to obtain a catalyst wet material, and drying the catalyst wet material at a low temperature of 70 ℃ by microwaves for 4.5 hours to obtain the integral honeycomb ceramic catalyst. And (3) asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials, and calcining at 550 ℃ for 4.5 hours to prepare the wall-flow type integrated extrusion formed sulfur trapping catalyst, which is marked as sample 4.
Example 5
Into the mixer according to Ca/5A (molar ratio of silicon to aluminum=3): na/OFF (molar ratio of silicon to aluminum=5): modified alumina (wt% ai 2 o3=95%, wt% NO3- =5%): ca (NO 3) 2: ni (NO 3) 2: sesbania powder = 14%:24%:11%:4%:1.5%:2% and dry-blending continuously until uniform. To the dry mix was added concentrated nitric acid solution (concentration 63%): concentrated hydrochloric acid: h2o=1.5%: 0.5%: the 41% portion was added to the mixer uniformly and slowly and wet mixed for 0.5h. After the wet materials are uniformly mixed, 0.5 percent polyethylene glycol (polymerization degree 4000) is added, after the wet mixing is continued for 2 hours, the pug is put into a vacuumizing pugging machine for pugging, and vacuumizing and pugging are carried out for 4 times. Putting the well-kneaded pug into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, cutting the blank into a required height to obtain a catalyst wet material, and drying the catalyst wet material at a low temperature of 70 ℃ by microwaves for 4.5 hours to obtain the integral honeycomb ceramic catalyst. And (3) asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials, and calcining at 550 ℃ for 4.5 hours to prepare the wall-flow type integrated extrusion formed sulfur trapping catalyst, which is marked as sample 5.
Comparative example 1
The sulfur trap catalyst was prepared according to the sulfur trap catalyst preparation method of CN1234473 a.
500g of gamma-Al 2O3 is weighed and dissolved in deionized water, 1182g of MgO is added into the suspension after uniform stirring, 1150g of Al2O3 powder is added after stirring for 30min, and the suspension is pre-calcined for 4 hours at 550 ℃ after uniform stirring. The dispersion was impregnated on a cordierite support of honeycomb structure at a loading of 170g/L by an impregnation method, dried at 120℃and calcined at 500℃for 2 hours. The coated honeycomb ceramic was immersed in tetramine platinum nitrate, dried, and then calcined in air at 500 ℃ for 2 hours to prepare a sulfur trap catalyst, which was designated as "sample 6".
After the samples 1-6 are packaged completely, the initial weight is weighed and then the sample is arranged on a six 4L diesel engine bench, wherein a sulfur catcher is arranged at the 10cm position of the front end of a DOC, the bench adopts fuel oil with different sulfur contents of 2000ppm, 1500ppm, 350ppm, 50ppm and 10ppm, a sulfur catcher catalyst is arranged at the upstream of a six-grade treatment catalyst of the state, according to the requirements of reference heavy diesel vehicle pollutant emission limit and measurement method (Chinese sixth stage) (GB 17691-2018), WHTC circulation working condition test is carried out, the tail gas of the ASC rear end is connected with an analyzer, SO2 and other gaseous pollutant concentrations are collected, after the SO2 concentration exceeding 20ppm is detected, the engine operation is stopped, and after the sulfur catcher is disassembled, the sample is subjected to heat preservation at 100 ℃ for 30min in an oven and then weighed.
The post-treatment catalyst is detached, the national standard No. 0 diesel oil is used, a tail pipe is connected with an analyzer, and the emission quantity (g/kWh) of the source emission NOx is calculated by weighting according to the requirement of regulations after the WHTC-H circulation working condition test thermal state circulation test is finished and according to the requirement of the ' heavy diesel vehicle pollutant emission limit value and the measuring method (the sixth stage of China ' (GB 17691-2018 ').
After the source exhaust test is finished, the post-treatment catalyst is installed, the national standard No. 0 diesel is used, an analyzer is connected to a tail pipe at the rear end of the ASC catalyst, and the tail exhaust NOx emission (g/kWh) is calculated in a weighting manner according to the requirements of the heavy diesel vehicle pollutant emission limit and measurement method (Chinese sixth stage) (GB 17691-2018) after the WHTC-H circulation working condition test thermal state circulation test is finished.
The catalysts obtained in examples 1 to 5 and comparative example 1 were subjected to a cycle emission test and sulfur capacity calculation, respectively, by the following methods:
1) The sulfur capacity of the catalyst is calculated according to the following formula:
。
wherein m1 represents the mass after accumulation of sulfur (g), m0 represents the initial mass of catalyst (g), and V represents the sulfur trap catalyst volume (L);
2) The catalyst NOx conversion efficiency is calculated as follows:
。
wherein, the NOx tail emission and the NOx source emission respectively represent the NOx emission (g/kWh) of the tail emission and the source emission of the engine under the WHTC-H cycle.
Fig. 2 shows the X-ray diffraction (XRD) results of the sulfur trap catalyst prepared in example 1 of the present invention, and it is understood from the test results that the sulfur trap catalyst prepared in example 1 has typical hexagonal alkaline OFF diffraction peaks, and no Ba and Ce metal species are detected, indicating that the Ba and Ce metal species are highly dispersed in the OFF crystal or do not reach the XRD detection limit. The OFF pore size is the 12-ring barrier-free macropore of 7A x 7A, SO that abundant reaction sites are provided for the reaction of SO2 and SO3 with framework cations Na+, K+ and alkaline oxides, and sulfide trapping efficiency is improved.
Fig. 3 is the results of NOx conversion efficiency and sulfur capacity for the catalysts of inventive examples 1, 2, 3, 4, 5, and comparative example 1. As can be seen from the comparison of FIG. 1, by arranging the high-efficiency sulfur capturing catalyst device at the upstream of the catalyst, the catalyst adopts the macroporous molecular sieve as a carrier, alkaline earth metal and transition metal as active components, the sulfur capacity of the catalyst can be up to 180-300g/cat, the service cycle is long, SO2 and sulfate species can be efficiently captured, and pollution of sulfur oxides to the post-treatment catalyst under different application scenes can be effectively prevented. The Na-type, ca-type, K-type, na/K-type OFF, 4A, 5A and 13X porous molecular sieve materials are adopted, so that the pore canal of the macroporous molecular sieve and the active single-site, double-site and three-site combined sulfur oxides can be effectively utilized, and the purpose of capturing the sulfur oxides is achieved. Whereas the catalyst of comparative example 1 can only reach a sulfur capacity of about 100g/cat.
The above-described embodiments are merely some, but not all embodiments of the present invention. All other embodiments, which are the same or equivalent to the present disclosure, can be made by one skilled in the art based on the embodiments of the present disclosure without making any inventive effort, are intended to be within the scope of the present disclosure.
Claims (10)
1. The preparation method of the sulfur trapping catalyst for the diesel engine is characterized by comprising the following steps of: modified alumina: alkali metal salts: transition metal salts: extrusion aid: pore-forming agent: inorganic strong acid peptizing agent: h 2 O=33-40%: 8-13%:3-5%:1.5-3%:2-4.5%:0.5-1%:2-6%: and (3) uniformly mixing 27.5-50% by mass percent to obtain catalyst pug, extruding the catalyst pug to form, drying and calcining to obtain the sulfur trapping catalyst.
2. The method for preparing a sulfur trap catalyst for a diesel engine according to claim 1, wherein the molecular sieve is a powder material, including but not limited to one or two of OFF, 4A, 5A, 13X.
3. The method for producing a sulfur trap catalyst for a diesel engine according to claim 1 or 2, wherein the molecular sieve is one or a combination of two of Ca type, K type, na/K type; the molar ratio of silicon dioxide to aluminum oxide in the molecular sieve is less than or equal to 10:1, wherein Ca, K, na, na/K cations are coordinated with framework Al, and the molar ratio of alkali metal elements to Al elements is less than or equal to 0.85:1.
4. The method for preparing a sulfur trap catalyst for a diesel engine according to claim 1, wherein the modified alumina has a boehmite crystal structure, a grain size of 1 μm or less, an alumina content of 95% or more, and NO 3 - The content is less than or equal to 5 percent.
5. The method for preparing a sulfur trap catalyst for a diesel engine according to claim 1, wherein the alkali metal salt is nitrate obtained by adding an alkali metal element into nitric acid, and the purity of the nitrate is not less than 95%; the alkali metal element is one or two of Ca, mg and Ba.
6. The method for preparing a sulfur trap catalyst for a diesel engine according to claim 1, wherein the transition metal salt is nitrate obtained by adding transition metal elements into nitric acid, and the purity of the nitrate is not less than 95%; the transition metal element is one or two of Fe, co, ce, ni.
7. The method for preparing sulfur trapping catalyst for diesel engine according to claim 1, wherein the extrusion aid is one or more of hydrophilic carboxymethyl cellulose, starch, glycerol and hydroxyethyl cellulose, and the viscosity of the extrusion aid is 1500-3000 mpa.s.
8. The method for preparing sulfur trapping catalyst for diesel engine according to claim 1, wherein the pore-forming agent is one or more of polyethylene glycol, carbon powder and polyvinyl alcohol, and the polymerization degree of the pore-forming agent is 4000-6000.
9. The method for preparing sulfur trap catalyst for diesel engine according to claim 1, wherein the inorganic strong acid peptizing agent is one or two of concentrated nitric acid and concentrated hydrochloric acid.
10. The method for producing a sulfur trap catalyst for a diesel engine according to claims 1 to 9, characterized by comprising the steps of:
(1) Adding molecular sieve, modified alumina, alkali metal salt, transition metal salt and extrusion aid into a mixer, and continuously dry-mixing for 0.5-1h until uniformity;
(2) Adding an inorganic strong acid peptizing agent and H into the dry blend prepared in the step (1) 2 O, wet mixing for 0.5-1h;
(3) After the wet mixing in the step (2) is completed, adding a pore-forming agent, continuing the wet mixing for 1-1.5h to obtain pug, putting the pug into a vacuumizing pug mill, and vacuumizing and mixing for 3-5 times;
(4) Putting the pug which is well treated in the step (3) into a high-pressure vacuum extruder for extrusion molding to obtain a blank, molding the blank by using a mold, and cutting according to the required height to obtain a catalyst wet material;
(5) Drying the wet catalyst material prepared in the step (4) at a low temperature of 35-50 ℃ by microwaves to obtain an integral honeycomb ceramic catalyst;
(6) Asymmetrically plugging the air inlet end face and the air outlet end face of the integral honeycomb ceramic catalyst by using plugging materials;
(7) And (3) calcining the integral honeycomb ceramic catalyst subjected to hole blocking at a high temperature, and calcining at 550-650 ℃ for 3-5 hours to obtain the wall-flow type integrated extrusion molding sulfur trapping catalyst.
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| DE3808740A1 (en) * | 1988-03-16 | 1989-09-28 | Bayer Ag | Process for preparing a catalyst for the hydroconversion of hydrocarbons |
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| CN113634277A (en) * | 2021-08-13 | 2021-11-12 | 无锡威孚环保催化剂有限公司 | Preparation method of wall-flow type particle trapping catalyst |
| CN115869992A (en) * | 2022-12-21 | 2023-03-31 | 山东中移能节能环保科技股份有限公司 | Coking flue gas desulfurization and denitrification catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3808740A1 (en) * | 1988-03-16 | 1989-09-28 | Bayer Ag | Process for preparing a catalyst for the hydroconversion of hydrocarbons |
| CN101555821A (en) * | 2008-04-12 | 2009-10-14 | 德国曼商用车辆股份公司 | Sulphur resistant waste gas treatment system to oxidise no |
| CN102585493A (en) * | 2010-12-28 | 2012-07-18 | 上海杰事杰新材料(集团)股份有限公司 | Nano particle/polyamide composite material, preparation method and application thereof |
| CN113634277A (en) * | 2021-08-13 | 2021-11-12 | 无锡威孚环保催化剂有限公司 | Preparation method of wall-flow type particle trapping catalyst |
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