CN112516989A - Coating material catalyst and preparation method and application thereof - Google Patents
Coating material catalyst and preparation method and application thereof Download PDFInfo
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- CN112516989A CN112516989A CN202011527313.4A CN202011527313A CN112516989A CN 112516989 A CN112516989 A CN 112516989A CN 202011527313 A CN202011527313 A CN 202011527313A CN 112516989 A CN112516989 A CN 112516989A
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- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 85
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000004071 soot Substances 0.000 claims abstract description 25
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 17
- 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 claims abstract description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 12
- GESWHEKGODWMHD-UHFFFAOYSA-N [Pr].[La] Chemical compound [Pr].[La] GESWHEKGODWMHD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- 239000010970 precious metal Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract 3
- 230000008020 evaporation Effects 0.000 claims abstract 2
- 239000002002 slurry Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 49
- 239000011265 semifinished product Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 229910052708 sodium Inorganic materials 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 238000012360 testing method Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 16
- 229910001593 boehmite Inorganic materials 0.000 claims description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 14
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 14
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 230000002572 peristaltic effect Effects 0.000 claims description 10
- 238000001238 wet grinding Methods 0.000 claims description 10
- 208000005374 Poisoning Diseases 0.000 claims description 9
- 231100000572 poisoning Toxicity 0.000 claims description 9
- 230000000607 poisoning effect Effects 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 6
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 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 5
- 239000011324 bead Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- -1 lanthanum praseodymium modified aluminum oxide Chemical class 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 36
- 238000007254 oxidation reaction Methods 0.000 abstract description 36
- 230000008929 regeneration Effects 0.000 abstract description 18
- 238000011069 regeneration method Methods 0.000 abstract description 18
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 150000001340 alkali metals Chemical class 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 60
- 239000011734 sodium Substances 0.000 description 22
- 229910052700 potassium Inorganic materials 0.000 description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 18
- 239000011591 potassium Substances 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 229910052596 spinel Inorganic materials 0.000 description 10
- 239000011029 spinel Substances 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000779 smoke Substances 0.000 description 7
- 244000205754 Colocasia esculenta Species 0.000 description 6
- 235000006481 Colocasia esculenta Nutrition 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 239000006255 coating slurry Substances 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- F01N3/24—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 characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (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
本发明公开了一种涂层材料催化剂及其制备方法和应用，涉及DPF催化剂领域，本发明公开了使用镧镨改性氧化铝作为载体，负载碱金属、过渡金属和贵金属作为主催化剂和催化助剂，通过采用注射滴加的方式将碱金属负载于氧化铝上，以闪蒸的方式进行快速干燥，再经回转煅烧炉进行高温焙烧，最后负载上过渡金属和贵金属作为主催化剂，从而获得一款高效氧化涂层材料，涂敷于堇青石材料或碳化硅材料的颗粒捕集器DPF上，来大幅提升DPF氧化碳烟的转化效率。本发明能够解决现有技术中涂层材料催化剂再生效率较低、再生里程较短、再生温度较高以及生产成本较高的问题。
The invention discloses a coating material catalyst, a preparation method and application thereof, and relates to the field of DPF catalysts. The invention discloses the use of lanthanum praseodymium modified alumina as a carrier, and supported alkali metals, transition metals and precious metals as main catalysts and catalytic promoters Alkali metal is supported on alumina by injection and dropwise addition, fast drying is carried out by flash evaporation, and then high temperature calcination is carried out in a rotary calciner, and finally transition metals and precious metals are loaded as main catalysts, thereby obtaining a This high-efficiency oxidation coating material is coated on the particle filter DPF of cordierite material or silicon carbide material to greatly improve the conversion efficiency of DPF oxidized soot. The invention can solve the problems of low regeneration efficiency, short regeneration mileage, high regeneration temperature and high production cost of the coating material catalyst in the prior art.
Description
Technical Field
The invention relates to the field of DPF catalysts, in particular to a coating material catalyst and a preparation method and application thereof.
Background
The invention relates to a DPF catalyst suitable for treating PM of automobile exhaust pollutants of six-diesel-engine vehicles in the road country and four-stage vehicles in the non-road, wherein a particle catcher is used as a device for collecting and filtering soot in a diesel engine automobile exhaust gas treatment device.
Diesel exhaust contains a large amount of pollutants, the key of which is how to reduce PM. PM is soot which is a product of incomplete combustion of diesel engine fuel and contains a large amount of black carbon particles; instead of pure carbon, it is a polymer whose main component varies slightly with the load of the diesel engine, and generally contains 85-95% of C, 4-8% of O and a small amount of H and ash. Soot is also considered to be a graphite crystal and is composed of porous carbon particles having a diameter of about 0.05 μm and aggregated into a size of 0.1 to 10 μm.
The oxidation efficiency of the coating material on the market at present for soot is shown as the following two points: firstly, the conversion efficiency of the coating is not high, so that the regeneration mileage of the DPF is too short, the active regeneration is triggered by a common road vehicle at about 500 kilometers, and higher temperature (more than 600 ℃) is required; secondly, the price is high, and the loading capacity of the precious metal is required to reach more than 5-10 g/cft.
It is desired to prepare DPF catalysts by using catalysts having high passive regeneration efficiency, long regeneration course and low cost, and by simplifying the preparation method and process conditions.
Disclosure of Invention
The invention aims to solve the technical problems of low regeneration efficiency, short regeneration mileage, high regeneration temperature and high production cost of a coating material catalyst in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a coating material catalyst comprises the following steps:
s1: adding lanthanum praseodymium modified aluminum oxide material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then, injecting and dropwise adding an alkali solution into the alumina slurry through a peristaltic pump, wherein the dropwise adding time is controlled to be 60-90 minutes, the pH value of the slurry is adjusted to be maintained between 3.8-4.2 through nitric acid in the process, the stirring time is controlled to be 3.0-5.0 hours, a mixed solution A is formed, the mass proportion of the lanthanum oxide and the praseodymium oxide in the lanthanum praseodymium modified alumina material is 1.0-4.0%, and the surface area of the lanthanum oxide and praseodymium oxide meets the requirement that the test value is not less than 150 m after the lanthanum oxide and the praseodymium oxide are thermally aged for 4 hours under the aging condition of 1000 DEG C2The alkaline solution is carbonate solution of any one or more of Na, Cs, Ba, K, Li and Mg, and the mass ratio of carbonate in the carbonate solution to alumina in the alumina slurry is 1:8-1: 9;
s2: drying the mixed solution A at 100-150 ℃ by a spray flash dryer, and controlling the feeding rate in the drying process to ensure that the drying efficiency is 95-98% to obtain powder B;
s3: calcining the powder B at high temperature through a rotary calciner, controlling the final temperature at 900-1000 ℃ at a programmed heating rate of 5 ℃/min, keeping the temperature for 4.0-6.0 h, and supplementing air for atmosphere protection in the calcining process;
s4: preparing calcined powder into slurry C through wet grinding, and controlling the detected granularity D50 in the slurry C to be 2.5-3.0 mu m;
s5: mixing a transition metal nitrate and a precious metal nitrate in deionized water, injecting the mixture into the slurry C through a peristaltic pump, controlling the dropping time to be 60-90 minutes, adjusting the pH value of the slurry liquid to be maintained between 3.8-4.2 through ammonia water in the process, and controlling the stirring time to be 1.0-2.0 hours to obtain slurry D, wherein the transition metal nitrate is any one or more of Cu, Co, Mn, Fe, V, Sn, Ni and W, the ratio of the transition metal nitrate to the amount of alumina in the alumina slurry is 0.03-0.06, and the ratio of the precious metal nitrate to the amount of alumina in the alumina slurry is 0.005-0.01;
s6: controlling the solid content of the slurry D to be 10% -14%, adding boehmite powder, then adding hydroxymethyl cellulose, and stirring for 30-60 minutes to obtain slurry E, wherein the mass ratio of the boehmite powder to the alumina in the slurry D is 1:100-2:100, and the mass ratio of the hydroxymethyl cellulose to the alumina in the slurry D is 4: 100-6: 100, respectively;
s7: selecting a semi-permeable carrier with an NGK 300-10 silicon carbide asymmetric structure or a semi-permeable carrier with an NGK 300-9 cordierite asymmetric structure, selecting a semi-edge air inlet end for coating, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
s8: carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
s9: carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
Further, the precursor of the lanthanum praseodymium modified alumina selected in the step S1 is of a lanthanum praseodymium aluminum common structure, the forming and baking temperature of the precursor of the lanthanum praseodymium modified alumina is not less than 950 ℃, the time is not less than 5.0h, and the impurity content is controlled to be not more than 1.0%.
Further, the alkali solution in step S1 is a carbonate solution of at least two of Na, Cs, Ba, K, Li, and Mg.
Further, the mass ratio of the carbonate in the carbonate solution to the alumina in the alumina slurry in the step S1 is 1:8.5-1: 9.
Further, in the step S1, deionized water is added into the reaction kettle, the heating temperature is controlled to be 40-60 ℃, and then lanthanum-modified alumina powder is added into the deionized water, wherein the PH is maintained at 3.9-4.1 and the temperature is maintained at 40-60 ℃.
Further, in the step S2, the spray flash dryer uses a laboratory type spray drying device, the power is 4.0kw, the inlet air temperature is 120-.
Further, in the step S3, during the high-temperature calcination, the temperature is first raised to 200 ℃ and maintained for 1.0 hour, the bound water is evaporated, and then raised to 600 ℃ and maintained for 2.0 hours, and the pre-calcination process is performed. Then the temperature is raised to 950 ℃ and 1000 ℃ and kept constant for 4.0-5.0 h.
Further, when wet grinding is performed in step S4, a horizontal sand mill is used for grinding, zirconia beads with a particle size of 1.0-1.2mm are used, the volume of the grinding cavity is 0.5L, the filling amount of the zirconia beads is 70-75% of the total volume, and the power is 2.2 kw.
Further, in step S4, a laser particle size analyzer is used to perform particle size detection analysis, a refractive index of 1.544 is selected during the test, the light shielding rate of the particle addition amount is 13-15%, ultrasonic waves are used to perform dispersion, and the dispersion time is three minutes.
Further, in step S5, iron nitrate is first added to the deionized water, nickel nitrate is then added to the deionized water, and platinum nitrate is then added to the deionized water.
Further, in the step S5, the stirring time is 60 to 70 min.
Further, in the step S6, the solid content of the slurry D is controlled to be 10%, the mass ratio of boehmite to the molecular sieve is 1:100, and the mass ratio of cellulose to the molecular sieve is 6: 100.
Further, in the step S7, the coating is performed by a lower feeding manner and feeding is performed at a single-side air inlet end, the drying temperature is 100-.
The invention also provides a coating material catalyst which is prepared by any one of the preparation methods of the coating material catalyst.
The invention also provides application of the coating material catalyst, and the coating material catalyst used for quickly oxidizing the carbon smoke on the DPF is applied to purification of the carbon smoke in tail gas of a national six-diesel engine vehicle type and a non-road four-stage vehicle type.
The invention has the following beneficial effects:
the coating material prepared by the preparation method has the advantages of high catalyst regeneration efficiency, long regeneration mileage, low regeneration temperature, andthe production cost is low. The coating material catalyst has the main advantages of good passive regeneration capacity for carbon smoke and good sulfur resistance stability. The coating material catalyst has strong hydrothermal aging performance, has a large specific surface area of a spinel structure, and simultaneously provides NO and NO according to the engine2The oxidation efficiency of the DPF catalyst on the carbon smoke is improved, so that the regeneration mileage of the DPF can be prolonged to 1500-2500 kilometers, and the long-time stable use of the DPF is realized. The high-efficiency oxidation coating DPF catalyst prepared by the method has simple preparation procedures because no waste materials are generated in the process; and contains more alkali metals and transition metals, so the catalyst has lower sensitivity to sulfur and has better sulfur poisoning resistance. The high-efficiency oxidation coating DPF catalyst prepared by the invention has the BET specific surface area of 50-80m2The catalyst has good water-resistant thermal stability, and the oxidation efficiency of PM can reach more than 50% at 400 ℃.
Drawings
FIG. 1 is a composition diagram of particle size of black smoke particles of a national six-diesel engine;
FIG. 2 is a graph of trapping efficiency without coating for a 300-10 silicon carbide asymmetric support of NGK or a 300-9 cordierite asymmetric support of NGK;
FIG. 3 is a graph of soot conversion efficiency for example 1, comparative example 1, and comparative example 2;
FIG. 4 is a bench test plot of soot conversion efficiency for example 2, comparative example 3, and comparative example 4;
FIG. 5 shows a graph containing K2CO3A material performance advantage graph of (1);
FIG. 6 is a graph of heavy steam MC13 test data from a six-country engine rig;
FIG. 7 is a spectrum of K element scanning on a plane of the high efficiency oxidation coating powder using an electron scanning microscope for the catalyst of the present invention;
FIG. 8 is a graph of Fe element scanning on a plane of the high efficiency oxidation coating powder using an electron scanning microscope for the catalyst of the present invention;
FIG. 9 is a diagram showing the element ratios obtained by an electron scanning microscope for the catalyst of the present invention.
Detailed Description
The particle size composition of black smoke particles of a national six-diesel engine is shown in figure 1, wherein the PM quantity concentration is mainly concentrated on 5-50nm, and the mass concentration is mainly concentrated on 50-500 nm.
In order to meet the national regulatory standards for road and country six-diesel models, non-road four-stage models, it is necessary to select an appropriate particulate trap and a coated catalyst material that enables the DPF to be recycled for a long period of time.
According to the particle size of the particles discharged by the engine, 300-10 silicon carbide asymmetric carrier of NGK or 300-9 cordierite asymmetric carrier of NGK is selected as the selective carrier for trapping soot, and the trapping effect is shown in figure 2.
As can be seen from FIG. 2, the PM trapping efficiency of the 300-10 silicon carbide asymmetric support of NGK or the 300-9 cordierite asymmetric support of NGK without coating reached 90% or more.
To further improve the trapping efficiency, a coating material with fast-oxidizing soot is coated on 300-10 silicon carbide asymmetric support of NGK or 300-9 cordierite asymmetric support of NGK.
Example 1:
the coating material catalyst is prepared by the following steps:
(1) selecting 5.0% lanthanum praseodymium modified alumina produced by French Sonervai company, and aging at 1050 deg.C for 4 hr to obtain BET of 180 m2Alumina in a/g ratio as support material. Firstly, taking a proper amount of deionized water, heating to 40-60 ℃, and fully stirring; next, K is selected2CO3、Na2CO3As a potassium source and a sodium source, the weight ratio of the potassium source to the sodium source is 9: 1 to prepare an alkali solution; according to m (K)2CO3+Na2CO3):m(Al2CO3) Is 1:8.5-1:9, determining the dosage of the alumina and the dosage of the potassium source and the sodium source;
(2) adding the lanthanum-modified aluminum oxide material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then adding the alkali solution into the alumina slurry in an injection and dropwise manner by a peristaltic pump, controlling the dropwise adding time to be 60-90 minutes, adjusting the pH of the slurry liquid to be maintained between 3.8-4.2 by nitric acid in the process, and controlling the stirring time to be 3.0-5.0 hours;
(3) drying the prepared alumina solution containing sylvite and sodium salt by a spray flash dryer at the temperature of 100 ℃ and 150 ℃, and controlling the feeding rate to achieve the drying efficiency of 95-98 percent; performing high-temperature calcination on the dried powder through a rotary calciner, and finally controlling the temperature at 900-1000 ℃ at a temperature-programmed heating rate of 5 ℃/min for 4.0-6.0 h, wherein air is required to be supplemented in the process for atmosphere protection;
(4) preparing the calcined powder into slurry due to the formation of KAlO with spinel structure2Material to realize KAlO2-Al2O3The uniform mixing needs wet grinding, so that a slurry liquid with uniform particle size is obtained, and the subsequent loading of the main catalyst material is facilitated; controlling the solid content of the prepared slurry to be 10-12%, adding 1.0% (mass ratio to alumina) boehmite powder, adding 6.0% (mass ratio to alumina) hydroxymethyl cellulose, and stirring for 50-60 minutes to obtain wet high-efficiency oxidation coating slurry to be coated;
(5) selecting a semi-permeable carrier with an NGK 300-10 silicon carbide asymmetric structure or a semi-permeable carrier with an NGK 300-9 cordierite asymmetric structure, selecting a semi-edge air inlet end for coating, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
(6) carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
(7) carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
KAlO in example 1 of the present invention2-Al2O3The combined body material of (1) is formed by spinel with the concentration of nearly 10%Structure KAlO2And approximately 90% gamma-Al 203Through the connection of Al atoms.
The alkali metal material used in the catalyst of the present invention may be any one of alkali metal and alkaline earth metal families, and preferably contains Na, Cs, Ba, K, Li and Mg, except K, Na.
The transition metal raw material selected by the catalyst can be various B-group transition metal group elements such as Cu, Co, Mn, Fe, V, Sn, Ni and W.
The drying procedure in the preparation of the high-efficiency oxidation coating catalyst material adopts spray flash drying, and can realize rapid shaping of the loaded K, Na ions, thereby being beneficial to meeting the requirement of dispersion rate in finished products.
In order to enable reaction soot to be in close contact with the efficient oxidation coating of the catalyst, the carrier of the DPF catalyst can be a known cordierite asymmetric semi-permeable carrier or a silicon carbide asymmetric semi-permeable carrier. It is recommended to select either 300-9 cordierite carriers with NGK, or 300-10 silicon carbide carriers.
As one of the methods for supporting DPF catalysts, in the case where an asymmetric semi-permeable wall flow type carrier made of cordierite is used for supporting, when the DPF carrier oxidizes soot, it is preferable to support the catalyst at a loading amount of 15 to 20g/L in order to ensure sufficiently high oxidation efficiency and regeneration mileage of the catalyst. Not only ensures the conversion efficiency, but also has lower cost.
Suitable for use as a supported binder for DPF catalysts, boehmite and hydroxymethylcellulose are preferably selected. The addition amount of boehmite is 1.0% of the mass fraction of the molecular sieve, and the best is cellulose with the mass fraction of 6.0%.
The catalyst of the present invention is obtained by observing the change in intensity of an electron beam with a scanning electron microscope and analyzing the composition of a substance based on information such as secondary electrons, absorbed electrons, and X-rays generated by the interaction between the electron beam and the substance, thereby obtaining the ratio of each element. The test results are shown in fig. 9.
The catalyst of the invention is fully called X-ray diffraction (X-ray diffraction) by XRD analysis equipment, and the diffraction phenomenon of X-rays in crystals is utilized to obtain the signal characteristics of the diffracted X-rays, and a diffraction pattern is obtained after processing. The spectrogram information can be used for determining a phase of a conventional microscope, and a 'perspective eye' is provided to judge whether defects (dislocation), lattice defects and the like exist in the crystal so as to judge the crystal structure type of the material.
According to XRD test results, the material has 70% of Al2O3 and 28.5% of KAl5O8 crystal structure, and KAl4O8, namely KAlO2-2Al2O3 structure, which indicates that potassium metaaluminate with a spinel structure is formed.
For the catalyst of the present invention, an electron scanning microscope is used to scan a certain plane of the high-efficiency oxidation coating powder by K element, and a spectrum shown in fig. 7 can be obtained.
For the catalyst of the present invention, an electron scanning microscope is used to scan Fe element on a certain plane of the high efficiency oxidation coating powder, and a spectrum shown in fig. 8 can be obtained.
From the scan data on the graph, the dispersion ratio values of the active ingredients can be calculated.
The catalyst of the present invention was prepared by weighing 40mg of a sample, degassing the sample at 200 ℃ and measuring the BET specific surface area by a nitrogen physical adsorption method (Shimadzu, Japan).
3mL of HF and 3mL of HNO3 were added to 50mg of the catalyst, and the mixture was dissolved in a microwave oven, and then nitric acid was added to the residue to sufficiently dissolve the residue. Inductively coupled plasma atomic emission spectrometry (ICP-AES), composition analysis of the catalyst components was performed on the solution.
The gas composition of the tail gas was simulated by using an FT-1R analyzer, and the reaction temperatures were set to 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃ and NO2The oxidation combustion efficiency of the high-efficiency oxidation coating on soot was determined under the conditions that the ratio of NOx was 20% and the space velocity was 60000 h-1.
A heavy steam MC13 engine of the national six standard is selected for efficiency testing, the temperatures of 300 ℃, 350 ℃, 400 ℃, 500 ℃ and 600 ℃ are respectively selected for testing, and the oxidation combustion efficiency of the efficient oxidation coating on the soot is measured, as shown in figure 6.
Comparative example 1:
adopting pure alumina, and aging at 1050 ℃ for 4h to obtain BET test value less than 100 m2The material per gram is used for preparing the coating material catalyst according to the following steps:
(1) firstly, taking a proper amount of deionized water, heating to 40-60 ℃, and fully stirring; next, K is selected2CO3、Na2CO3As a potassium source and a sodium source, the weight ratio of the potassium source to the sodium source is 9: 1 to prepare an alkali solution; according to m (K)2CO3+Na2CO3):m(Al2CO3) Is 1:8.5-1:9, determining the dosage of the alumina and the dosage of the potassium source and the sodium source;
(2) aging at 1050 deg.C for 4 hr to obtain BET test value less than 100 m2Adding per gram of pure alumina material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then adding the alkali solution into the alumina slurry in an injection and dropwise manner by a peristaltic pump, controlling the dropwise adding time to be 60-90 minutes, adjusting the pH of the slurry liquid to be maintained between 3.8-4.2 by nitric acid in the process, and controlling the stirring time to be 3.0-5.0 hours;
(3) drying the prepared alumina solution containing sylvite and sodium salt by a spray flash dryer at the temperature of 100 ℃ and 150 ℃, and controlling the feeding rate to achieve the drying efficiency of 95-98 percent; performing high-temperature calcination on the dried powder through a rotary calciner, and finally controlling the temperature at 900-1000 ℃ at a temperature-programmed heating rate of 5 ℃/min for 4.0-6.0 h, wherein air is required to be supplemented in the process for atmosphere protection;
(4) preparing the calcined powder into slurry, wherein the KalO2 material with a spinel structure is formed, so that wet grinding is needed to realize uniform mixing of KAlO2-Al2O3, thereby obtaining slurry liquid with uniform particle size, and facilitating subsequent loading of the main catalyst material; controlling the solid content of the prepared slurry to be 10-12%, adding 1.0% (mass ratio to alumina) boehmite powder, adding 6.0% (mass ratio to alumina) hydroxymethyl cellulose, and stirring for 50-60 minutes to obtain wet high-efficiency oxidation coating slurry to be coated;
(5) selecting a semi-permeable carrier with an NGK 300-10 silicon carbide asymmetric structure or a semi-permeable carrier with an NGK 300-9 cordierite asymmetric structure, selecting a semi-edge air inlet end for coating, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
(6) carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
(7) carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
Comparative example 2:
the coating material catalyst is prepared by adopting an alumina material modified by 10 percent of lanthanum and aged for 4 hours at 1050 ℃ and with a BET test value of less than 100 m2/g according to the following steps:
(1) firstly, taking a proper amount of deionized water, heating to 40-60 ℃, and fully stirring; next, K is selected2CO3、Na2CO3As a potassium source and a sodium source, the weight ratio of the potassium source to the sodium source is 9: 1 to prepare an alkali solution; according to m (K)2CO3+Na2CO3):m(Al2CO3) Is 1:8.5-1:9, determining the dosage of the alumina and the dosage of the potassium source and the sodium source;
(2) modifying 10% lanthanum, aging at 1050 deg.C for 4h, and testing BET value less than 100 m2Adding per gram of aluminum oxide material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then adding the alkali solution into the alumina slurry in an injection and dropwise manner by a peristaltic pump, controlling the dropwise adding time to be 60-90 minutes, adjusting the pH of the slurry liquid to be maintained between 3.8-4.2 by nitric acid in the process, and controlling the stirring time to be 3.0-5.0 hours;
(3) drying the prepared alumina solution containing sylvite and sodium salt by a spray flash dryer at the temperature of 100 ℃ and 150 ℃, and controlling the feeding rate to achieve the drying efficiency of 95-98 percent; performing high-temperature calcination on the dried powder through a rotary calciner, and finally controlling the temperature at 900-1000 ℃ at a temperature-programmed heating rate of 5 ℃/min for 4.0-6.0 h, wherein air is required to be supplemented in the process for atmosphere protection;
(4) preparing the calcined powder into slurry due to the formation of KAlO with spinel structure2Material to realize KAlO2-Al2O3The uniform mixing needs wet grinding, so that a slurry liquid with uniform particle size is obtained, and the subsequent loading of the main catalyst material is facilitated; controlling the solid content of the prepared slurry to be 10-12%, adding 1.0% (mass ratio to alumina) boehmite powder, adding 6.0% (mass ratio to alumina) hydroxymethyl cellulose, and stirring for 50-60 minutes to obtain wet high-efficiency oxidation coating slurry to be coated;
(5) selecting a semi-permeable carrier with an NGK 300-10 silicon carbide asymmetric structure or a semi-permeable carrier with an NGK 300-9 cordierite asymmetric structure, selecting a semi-edge air inlet end for coating, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
(6) carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
(7) carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
Comparing example 1 with comparative examples 1 and 2, the following data were obtained:
the DPF catalyst characteristics are compared as shown in the following table:
| BET | spinel structure ratio | Uniformity of active ingredient dispersion | |
| Example 1 | 102m2/g | 10.1% | 95% |
| Comparative example 1 | 30m2/g | 6.8% | 27% |
| Comparative example 2 | 60m2/g | 3.2% | 50% |
Soot oxidation performance test:
when the DPF catalyst body is brought into contact with the mixed gas having the following concentration (capacity) at a predetermined temperature, time, space velocity, and a predetermined amount of soot, the soot oxidation efficiency is calculated with respect to the amount of decrease in soot on the DPF catalyst. The test conditions are shown in the following table:
| CO | NO | NO2 | O2 | N2 | SV | soot |
| 300ppm | 320ppm | 80ppm | 10% | Balancing | 60000h-1 | 5g/L |
The test results are shown in FIG. 3.
Therefore, whether the aluminum oxide is modified by proper lanthanum praseodymium or not and whether the BET value after being aged for 4 hours at 1050 ℃ is 150-200 m2/g or not are very critical for determining the performance indexes, and the natural efficient oxidation coating has a larger difference for the efficiency of soot oxidation.
For coating the high-efficiency oxidation coating finished product slurry on an NGK cordierite 300-9 asymmetric semi-permeable wall flow type carrier, the solid content of the slurry is strictly controlled to be 10-12%, the granularity of the slurry is 2.5-3.0 mu m, the addition amount of hydroxymethyl cellulose is 6.0% of the mass fraction of alumina, and according to the distribution of the coating on the DPF carrier, the pressure drop change of a finished product and the final change of the oxidation efficiency of soot, the solid content, the granularity and the addition amount of cellulose are demonstrated to be required to be ensured so as to ensure that the DPF has higher soot oxidation efficiency, mileage regeneration and durability.
Example 2:
the coating material catalyst is prepared by the following steps:
(1) 5.0 percent of lanthanum praseodymium is selected for modification, and alumina with the BET of 180 m2/g after being aged for 4 hours at 1050 ℃ is used as a carrier material. Firstly, taking a proper amount of deionized water, heating to 40-60 ℃, and fully stirring; next, K is selected2CO3、Na2CO3As a potassium source and a sodium source, the weight ratio of the potassium source to the sodium source is 9: 1 to prepare an alkali solution; according to m (K)2CO3+Na2CO3):m(Al2CO3) Is 1:8.5-1:9, determining the dosage of the alumina and the dosage of the potassium source and the sodium source;
(2) adding the lanthanum-modified aluminum oxide material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then adding the alkali solution into the alumina slurry in an injection and dropwise manner by a peristaltic pump, controlling the dropwise adding time to be 60-90 minutes, adjusting the pH of the slurry liquid to be maintained between 3.8-4.2 by nitric acid in the process, and controlling the stirring time to be 3.0-5.0 hours;
(3) drying the prepared alumina solution containing sylvite and sodium salt by a spray flash dryer at the temperature of 100 ℃ and 150 ℃, and controlling the feeding rate to achieve the drying efficiency of 95-98 percent; performing high-temperature calcination on the dried powder through a rotary calciner, and finally controlling the temperature at 900-1000 ℃ at a temperature-programmed heating rate of 5 ℃/min for 4.0-6.0 h, wherein air is required to be supplemented in the process for atmosphere protection;
(4) preparing the calcined powder into slurry due to the formation of KAlO with spinel structure2Material to realize KAlO2-Al2O3The uniform mixing needs wet grinding, so that a slurry liquid with uniform particle size is obtained, and the subsequent loading of the main catalyst material is facilitated; controlling the detected granularity D50 to be 2.5-3.0 mu m, controlling the solid content of the prepared slurry to be 10-12%, adding 1.0% (mass ratio to alumina) of boehmite powder, then adding 6.0% (mass ratio to alumina) of hydroxymethyl cellulose, and stirring for 50-60 minutes to prepare wet high-efficiency oxidation coating slurry to be coated;
(5) adopting 190.5 × 152.4/300-9 cordierite DPF carrier, selecting half of air inlet end to coat, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
(6) carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
(7) carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
Example 2, the index parameters of the slurry are controlled as follows: the solid content is 10-12%, the granularity of the slurry is 2.5-3.0 μm, the addition amount of the hydroxymethyl cellulose is 6.0% of the mass fraction of the alumina, and the oxidation efficiency of the soot is changed according to the distribution of the coating on the DPF carrier, the pressure drop of a finished product and the final oxidation efficiency of the soot.
The method relates to parameter regulation and control of slurry liquid of a finished product efficient oxidation coating, control of cellulose addition proportion and the bridging effect of the coating on the wall surface of a DPF carrier, which is related to the surface tension value of the slurry on the wall surface of the carrier; the better the bridging effect of the coating on the DPF wall surface, the more and more uniform the coating is dispersed on the surface of the wall surface pore channel, the larger the contact area with the carbon smoke is, and the higher the oxidation efficiency is.
The method realizes the good distribution of the high-efficiency oxidation coating material on the pore canal of the DPF wall surface, and can ensure that the DPF has higher soot oxidation efficiency, regeneration mileage and durability by making process exploration and parameter fixation on the solid content, granularity and cellulose addition amount of slurry.
Comparative example 3:
modulating the particle size value of the slurry, and performing the following steps:
(1) 5.0 percent of lanthanum praseodymium is selected for modification, and alumina with the BET of 180 m2/g after being aged for 4 hours at 1050 ℃ is used as a carrier material. Firstly, taking a proper amount of deionized water, heating to 40-60 ℃, and fully stirring; next, K is selected2CO3、Na2CO3As a potassium source and a sodium source, the weight ratio of the potassium source to the sodium source is 9: 1 to prepare an alkali solution(ii) a According to m (K)2CO3+Na2CO3):m(Al2CO3) Is 1:8.5-1:9, determining the dosage of the alumina and the dosage of the potassium source and the sodium source;
(2) adding the lanthanum-modified aluminum oxide material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then adding the alkali solution into the alumina slurry in an injection and dropwise manner by a peristaltic pump, controlling the dropwise adding time to be 60-90 minutes, adjusting the pH of the slurry liquid to be maintained between 3.8-4.2 by nitric acid in the process, and controlling the stirring time to be 3.0-5.0 hours;
(3) drying the prepared alumina solution containing sylvite and sodium salt by a spray flash dryer at the temperature of 100 ℃ and 150 ℃, and controlling the feeding rate to achieve the drying efficiency of 95-98 percent; performing high-temperature calcination on the dried powder through a rotary calciner, and finally controlling the temperature at 900-1000 ℃ at a temperature-programmed heating rate of 5 ℃/min for 4.0-6.0 h, wherein air is required to be supplemented in the process for atmosphere protection;
(4) preparing the calcined powder into slurry due to the formation of KAlO with spinel structure2Material to realize KAlO2-Al2O3The uniform mixing needs wet grinding, so that a slurry liquid with uniform particle size is obtained, and the subsequent loading of the main catalyst material is facilitated; controlling the detected granularity D50 to be 4.0-4.5 mu m, controlling the solid content of the prepared slurry to be 10-12%, adding 1.0% (mass ratio to alumina) of boehmite powder, then adding 6.0% (mass ratio to alumina) of hydroxymethyl cellulose, and stirring for 50-60 minutes to prepare wet high-efficiency oxidation coating slurry to be coated;
(5) adopting 190.5 × 152.4/300-9 cordierite DPF carrier, selecting half of air inlet end to coat, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
(6) carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
(7) carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
Comparative example 4:
adjusting the adding proportion of the hydroxymethyl cellulose of the slurry, and performing the following steps:
(1) 5.0 percent of lanthanum praseodymium is selected for modification, and alumina with the BET of 180 m2/g after being aged for 4 hours at 1050 ℃ is used as a carrier material. Firstly, taking a proper amount of deionized water, heating to 40-60 ℃, and fully stirring; next, K is selected2CO3、Na2CO3As a potassium source and a sodium source, the weight ratio of the potassium source to the sodium source is 9: 1 to prepare an alkali solution; according to m (K)2CO3+Na2CO3):m(Al2CO3) Is 1:8.5-1:9, determining the dosage of the alumina and the dosage of the potassium source and the sodium source;
(2) adding the lanthanum-modified aluminum oxide material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then adding the alkali solution into the alumina slurry in an injection and dropwise manner by a peristaltic pump, controlling the dropwise adding time to be 60-90 minutes, adjusting the pH of the slurry liquid to be maintained between 3.8-4.2 by nitric acid in the process, and controlling the stirring time to be 3.0-5.0 hours;
(3) drying the prepared alumina solution containing sylvite and sodium salt by a spray flash dryer at the temperature of 100 ℃ and 150 ℃, and controlling the feeding rate to achieve the drying efficiency of 95-98 percent; performing high-temperature calcination on the dried powder through a rotary calciner, and finally controlling the temperature at 900-1000 ℃ at a temperature-programmed heating rate of 5 ℃/min for 4.0-6.0 h, wherein air is required to be supplemented in the process for atmosphere protection;
(4) preparing the calcined powder into slurry due to the formation of KAlO with spinel structure2Material to realize KAlO2-Al2O3The uniform mixing needs wet grinding, thereby obtaining a slurry liquid with uniform particle size, and being convenient for subsequent main catalyst materialsLoading of the material; controlling the detected granularity D50 to be 2.0-2.5 mu m, controlling the solid content of the prepared slurry to be 10-12%, adding 1.0% (mass ratio to alumina) of boehmite powder, adding 2.0% (mass ratio to alumina) of hydroxymethyl cellulose, and stirring for 50-60 minutes to prepare wet high-efficiency oxidation coating slurry to be coated;
(5) adopting 190.5 × 152.4/300-9 cordierite DPF carrier, selecting half of air inlet end to coat, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
(6) carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
(7) carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
Comparative experiments were carried out on example 2 with comparative examples 3 and 4:
the test conditions are introduced, and mainly comprise bench test equipment and a packaging part.
Introduction of bench test equipment:
| model number | QC-Q28 | Calibration power/rotation speed (kW/rpm) | 96kW/3000rpm |
| Number of cylinders | 4 | Maximum torque/speed (Nm/rpm) | 400/1400-2400 |
| Low idle speed (rpm) | 750 | Compression ratio | 17.5 |
| Cylinder diameter x stroke | 94*102 | Form of oil supply system | High-pressure common rail |
| Displacement (L) | 2.8 | After-cold temperature control requirement (. degree. C.) | 50 (fixed point) |
| High idle speed (rpm) | 3450 | Cooling method | Liquid cooling |
| Cylinder arrangement | In-line arrangement | System voltage (V) | 24 |
Introduction of catalyst information:
| size of the carrier | Mesh wall of carrier | Coating weight gain | |
| Example 2 | 190.5*152.4 | 300-9 | 18g/L |
| Comparative example 3 | 190.5*152.4 | 300-9 | 18g/L |
| Comparative example 4 | 190.5*152.4 | 300-9 | 18g/L |
The data shown in fig. 4 were obtained.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in any way, and those skilled in the art can make various changes and modifications to the equivalent embodiments without departing from the scope of the present invention, and all such changes, modifications, equivalents and improvements that can be made to the above embodiments without departing from the technical spirit of the present invention are within the spirit and principle of the present invention.
Claims (15)
1. The preparation method of the coating material catalyst is characterized by comprising the following steps of:
s1: adding lanthanum praseodymium modified aluminum oxide material into deionized water, controlling the final solid content to be 20-30%, and controlling the pH of the solution to be 3.8-4.2 in the adding process; then, injecting and dropwise adding an alkali solution into the alumina slurry through a peristaltic pump, wherein the dropwise adding time is controlled to be 60-90 minutes, the pH value of the slurry is adjusted to be maintained between 3.8-4.2 through nitric acid in the process, the stirring time is controlled to be 3.0-5.0 hours, a mixed solution A is formed, the mass proportion of the lanthanum oxide and the praseodymium oxide in the lanthanum praseodymium modified alumina material is 1.0-4.0%, and the surface area of the lanthanum oxide and praseodymium oxide meets the requirement that the test value is not less than 150 m after the lanthanum oxide and the praseodymium oxide are thermally aged for 4 hours under the aging condition of 1000 DEG C2The alkaline solution is carbonate solution of any one or more of Na, Cs, Ba, K, Li and Mg, and the mass ratio of carbonate in the carbonate solution to alumina in the alumina slurry is 1:8-1: 9;
s2: drying the mixed solution A at 100-150 ℃ by a spray flash dryer, and controlling the feeding rate in the drying process to ensure that the drying efficiency is 95-98% to obtain powder B;
s3: calcining the powder B at high temperature through a rotary calciner, controlling the final temperature at 900-1000 ℃ at a programmed heating rate of 5 ℃/min, keeping the temperature for 4.0-6.0 h, and supplementing air for atmosphere protection in the calcining process;
s4: preparing calcined powder into slurry C through wet grinding, and controlling the detected granularity D50 in the slurry C to be 2.5-3.0 mu m;
s5: mixing a transition metal nitrate and a precious metal nitrate in deionized water, injecting the mixture into the slurry C through a peristaltic pump, controlling the dropping time to be 60-90 minutes, adjusting the pH value of the slurry liquid to be maintained between 3.8-4.2 through ammonia water in the process, and controlling the stirring time to be 1.0-2.0 hours to obtain slurry D, wherein the transition metal nitrate is any one or more of Cu, Co, Mn, Fe, V, Sn, Ni and W, the ratio of the transition metal nitrate to the amount of alumina in the alumina slurry is 0.03-0.06, and the ratio of the precious metal nitrate to the amount of alumina in the alumina slurry is 0.005-0.01;
s6: controlling the solid content of the slurry D to be 10% -14%, adding boehmite powder, then adding hydroxymethyl cellulose, and stirring for 30-60 minutes to obtain slurry E, wherein the mass ratio of the boehmite powder to the alumina in the slurry D is 1:100-2:100, and the mass ratio of the hydroxymethyl cellulose to the alumina in the slurry D is 4: 100-6: 100, respectively;
s7: selecting a semi-permeable carrier with an NGK 300-10 silicon carbide asymmetric structure or a semi-permeable carrier with an NGK 300-9 cordierite asymmetric structure, selecting a semi-edge air inlet end for coating, controlling the loading amount to be 15-20g/L, and drying and roasting to obtain a catalyst semi-finished product F;
s8: carrying out hydrothermal aging treatment on the catalyst semi-finished product F under the treatment conditions of 800 ℃ and 20 hours, wherein the mass ratio of water to the catalyst semi-finished product F in the hydrothermal aging treatment is 1:10, so as to obtain a catalyst semi-finished product G;
s9: carrying out sulfur poisoning treatment on the catalyst semi-finished product G under the treatment condition of SO2200ppm，O210%，H2O10%, the temperature is 250 ℃, the time is 16H, and a catalyst finished product H is prepared.
2. The method of claim 1, wherein the precursor of the lanthanum praseodymium-modified alumina selected in the step S1 is a lanthanum praseodymium aluminum common structure, the forming and baking temperature of the precursor of the lanthanum praseodymium-modified alumina is not less than 950 ℃, the time is not less than 5.0h, and the impurity content is not more than 1.0%.
3. The method of claim 1, wherein the alkali solution in step S1 is a carbonate solution of at least two of Na, Cs, Ba, K, Li, and Mg.
4. The method of claim 1, wherein the mass ratio of the carbonate in the carbonate solution to the alumina in the alumina slurry in the step S1 is 1:8.5 to 1: 9.
5. The method for preparing the coating material catalyst according to claim 1, wherein in the step S1, the deionized water is added into the reaction kettle, the heating temperature is controlled to be 40-60 ℃, and then the lanthanum-modified alumina powder is added into the deionized water, wherein the PH is maintained at 3.9-4.1 and the temperature is maintained at 40-60 ℃.
6. The method for preparing a catalyst of a coating material according to claim 1, wherein in the step S2, the spray flash dryer uses a laboratory type spray drying device, the power is 4.0kw, the temperature of the inlet air is 120-150 ℃, and the evaporation capacity of water is 1.0-1.5 kg/h.
7. The method as claimed in claim 1, wherein in the step S3, the high temperature calcination is performed by first raising the temperature to 200 ℃ for 1.0h, evaporating the bound water, raising the temperature to 600 ℃ for 2.0h, performing the pre-calcination step, and then raising the temperature to 950 ℃ and 1000 ℃ for 4.0-5.0 h.
8. The method of claim 1, wherein the wet milling in step S4 is performed by using a horizontal sand mill, wherein zirconia beads with a particle size of 1.0-1.2mm are used, the volume of the milling chamber is 0.5L, the loading of the zirconia beads is 70-75% of the total volume, and the power is 2.2 kw.
9. The method of claim 1, wherein in step S4, the particle size detection analysis is performed by a laser particle size analyzer, the refractive index is 1.544, the light shielding rate is 13-15% of the particle addition amount, the dispersion is performed by ultrasonic waves, and the dispersion time is three minutes.
10. The method of claim 1, wherein in step S5, the iron nitrate is added to the deionized water, the nickel nitrate is added to the deionized water, and the platinum nitrate is added to the deionized water.
11. The method of claim 1, wherein the stirring time in step S5 is 60-70 min.
12. The method of claim 1, wherein in step S6, the solid content of slurry D is controlled to be 10%, the mass ratio of boehmite to molecular sieve is 1:100, and the mass ratio of cellulose to molecular sieve is 6: 100.
13. The method as claimed in claim 1, wherein in step S7, the coating is performed by a lower feeding method and single-side air inlet feeding, the drying temperature is 100-120 ℃, and the baking temperature is 600-650 ℃.
14. A coating material catalyst, characterized in that the coating material catalyst is prepared by the method for preparing the coating material catalyst according to any one of claims 1 to 13.
15. Use of a coating material catalyst according to claim 14 for purifying soot in exhaust gases of diesel engine models of six countries and non-road four-stage models.
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