CN1593756A - Preparation method of metal honeycomb supported catalyst - Google Patents
Preparation method of metal honeycomb supported catalyst Download PDFInfo
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- CN1593756A CN1593756A CN200410041178.7A CN200410041178A CN1593756A CN 1593756 A CN1593756 A CN 1593756A CN 200410041178 A CN200410041178 A CN 200410041178A CN 1593756 A CN1593756 A CN 1593756A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000000843 powder Substances 0.000 claims abstract description 32
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 27
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 10
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 8
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical group [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 7
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 7
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 229910019020 PtO2 Inorganic materials 0.000 abstract 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000003252 repetitive effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a kind of metal honeycomb supporter catalyst and its manufacturing method. The coating of catalyst manufactured by this method isn't deciduous easily, and it has nice burning starting ability and higher the tri-effect catalyst activity. And also it can purify the CO, HC and NOx in the vent gas simultaneously, and has the wider operatable window. The manufacturing of the metal honeycomb supporter catalyst can be described as follows: use the nickel-chrome stainless steel honeycomb (called simply as metal honeycomb supporter) as the first supporter, and the active aluminum oxide powder as the second supporter; otherwise, add bit of the oxidate of rare earth element such as CeO2, La2O3, ZrO2 and Y2O3 as the accelerator and stabilizer; the active component is mainly of PtO2, PdO or the combination of them.
Description
Technical field
The present invention relates to a kind of preparation method of metallic honeycomb substrate catalyst, be applied to the pollutant process field in the vehicle exhaust.
Background technology
Along with China's rapid economy development, automotive industry has become one of mainstay of China's economy, the output of China's motor vehicle and recoverable amount increase year after year fast, but because China's motor vehicle level of production is still lower, add that urban road construction does not catch up with the quick growth of vehicle guaranteeding organic quantity, cause many cities car completely for suffering from, traffic congestion becomes homely food, thereby more aggravated the discharge capacity of motor-vehicle tail-gas, motor vehicle emission pollutant is more and more higher to the municipal pollution rate, and the existing coal-smoke pollution in the past of China's municipal pollution changes the pollution based on vehicular emission into.Present many cities " automobile disaster " form, and polluters such as the CO in the vehicle exhaust, HC, NOx become the main source of urban atmospheric pollution especially.
Along with the enhancing of people's environmental consciousness and country strengthen the city atmospheric environment management energetically, the automobile emission standard increasingly stringent, so motor vehicle cold start emission (pernicious gas of discharging in most of blast pipe is to produce at the initial stage of cold-starting automobile) has been had higher requirement, catalytic conversion to CO, HC and NOx is lower at low temperatures but owing to the ceramic honeycomb carrier catalyst, the emission concentration of this moment is very high, becomes the importance that tail gas pollution of motor-driven vehicle is administered.As for ceramic honeycomb carrier Preparation of catalysts method, mainly be infusion process, sol-gel process etc.
Metal beehive carrier because have that thermal capacitance is little, the advantage of quick heating behind the cold start, polluter to the motor vehicle cold start emission has clean-up effect preferably, for this reason the compound catalytic purification system that adopts metallic honeycomb substrate catalyst to combine with the ceramic honeycomb carrier catalyst basically abroad.The employed catalytic converter of China's motor vehicle mostly adopts external import now, the external catalytic reactor that produces had formed relative monopoly position already in the garage of China, cost is higher, in order to save cost, the high-performance motor vehicle vent gas catalytic cleaner that exploitation has domestic independent intellectual property right, we have carried out relevant metallic honeycomb substrate catalyst Study on Preparation Technology.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of metallic honeycomb substrate catalyst, the coating difficult drop-off of the metallic honeycomb substrate catalyst of this method preparation, the ignition performance is good, has higher three-way catalyst activity, CO, HC, the NOx in the purifying exhaust gas simultaneously, but and the action pane of broad arranged.
Mainly be with nickel chromium stainless steel honeycomb (abbreviating metal beehive carrier as) as first carrier, the active oxidation aluminium powder is γ-Al
2O
3Be second carrier, also add the oxide such as the CeO of a small amount of rare earth element in addition
2, La
2O
3, ZrO
2, Y
2O
3As promoter and stabilizing agent; Active component is mainly PtO
2Or the combination of PdO or two kinds of materials.
The objective of the invention is to realize by following measure:
The preparation method of metallic honeycomb substrate catalyst may further comprise the steps:
A, processing: the nickel chromium stainless steel honeycomb carries out preliminary treatment as first carrier to this metal beehive carrier, promptly under 300～400 ℃ of temperature conditions roasting 1-3 hour;
B, preparation powdered form catalyst: the active oxidation aluminium powder that auxiliary agent, active constituent are added as second carrier is γ-Al successively
2O
3In carry out ball milling, make the powdered form catalyst:
At first, add the auxiliary agent that accounts for active oxidation aluminium powder gross weight 10-20%, ball milling 3-7 hour, wherein auxiliary agent is chosen and contained cerium oxide and lanthana, both weight ratio cerium oxide: lanthana was (1.6～3): (0.4～1);
Secondly, add the active constituent that accounts for active oxidation aluminium powder gross weight 1-4%, ball milling 3-7 hour, wherein active constituent is platinum oxide or palladium oxide or both by platinum oxide: palladium oxide was (2-3): the combination of 1 weight ratio;
At last, obtain the thinner powdered form catalyst that contains auxiliary agent of granularity;
C, preparation coating liquid: with above-mentioned powdered form catalyst and water by being 1: weight ratio (2-3.5) is mixed, fully stirs to make it to mix, and the interpolation small amount of acid, and the pH value of controlling slurries is 3-4;
With the slurries that make ball milling 8-15 hour again, make catalyst-coated liquid;
D, coating: with the dipping mode to the metal beehive carrier hanging, after hanging finishes coating liquid unnecessary in the metal beehive carrier is removed, subsequently the evenly oven dry under 100-300 ℃ of temperature of coated metal beehive carrier, time is 20-40min, then metal beehive carrier is put into Muffle furnace in 300-500 ℃ of roasting temperature 20-40min, and insulation 20-40min;
Once more to metal beehive carrier apply, oven dry, roasting, repeat at least 1-2 time;
E, roasting: the metal beehive carrier that will be loaded with catalyst-coated liquid at last places Muffle furnace in 350-650 ℃ of following roasting 2-7h, and insulation 8-15h.
Also contain in zirconia, the yittrium oxide one or both in the auxiliary agent, and the proportionate relationship of cerium oxide, lanthana: cerium oxide: lanthana: zirconia: yittrium oxide is (1.6～3): (0.4～1): (0～1): (0～0.1).
Platinum oxide and palladium oxide are to make by roasting chloroplatinic acid, palladium bichloride in the active constituent.
Regulate the pH value and adopt nitric acid.
The activated alumina molecular formula is γ-Al
2O
3
The hole density of metal beehive carrier: 200～400 orders, wall thickness 0.05～0.15mm, diameter are 30～200mm, length is 50～500mm; Metal beehive carrier is rolled into by special tinsel, inner uniform a large amount of duct, and the similar honeycomb ceramics of shape is so be called metal beehive carrier (also claiming the tinsel honeycomb substrate).The thermal-shock resistance of metal beehive carrier, freedom from vibration, ignition and gas fluidity are better, have that resistance is little, contact evenly, be difficult for characteristics such as thermal response is fast behind broken, the cold start, but the at present domestic catalyst that does not still have the employing metal beehive carrier as matrix, still carried out the Study on Preparation Technology of metallic honeycomb substrate catalyst.
The used rare earth of cleaning catalyst for tail gases of automobiles mainly is that wherein cerium oxide is crucial composition based on the mixture of cerium oxide, zirconia and lanthana etc.Because the redox characteristic of cerium oxide, the component of control discharging tail gas effectively, Ce has storage oxygen function, can oxygen supply in reducing atmosphere, or in oxidizing atmosphere oxygen consumption, and the dispersiveness of platinum etc. on can the rugged catalyst surface.Ceria also plays stabilization in noble metal atmosphere, to keep the catalyst advantages of high catalytic activity.La is alternative rhodium in platinum based catalyst, reduces cost.Under certain condition, noble metal catalyst and rare earth catalyst can make above three reactions carry out simultaneously, thereby have reached the purpose that purifies CO, HC and NOx simultaneously.Add high energy, the high temperature oxidation resistance that rare earth elements such as La, Ce, Y can also improve carrier in this external catalyst carrier.
Have following advantage according to the prepared catalyst of this preparation method:
(1) adhesiveness between metal beehive carrier and the catalyst-coated liquid is better, the coating difficult drop-off;
(2) low-temperature catalyzed performance is good, has lower initiation temperature;
(3) resistance to elevated temperatures is good;
(4) have higher three-way catalyst activity, CO, HC, the NOx in the purifying exhaust gas simultaneously, but the action pane of broad is arranged;
(5) noble metal dosage is few, and rhodium-containing not, and cost is lower.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is further elaborated:
Wherein, the molecular formula of activated alumina is γ-Al
2O
3, cerium oxide molecular formula be CeO
2, lanthana molecular formula be La
2O
3, zirconic molecular formula is ZrO
2, yittrium oxide molecular formula be Y
2O
3, the molecular formula of platinum oxide is PtO
2, palladium oxide molecular formula be PdO, the molecular formula of chloroplatinic acid is H
2PtCl
66H
2O, the molecular formula of palladium bichloride is PdCl
2
Embodiment one:
Select nickel chromium stainless steel honeycomb metallic carrier for use, hole density is 200 orders, and wall thickness 0.08mm, diameter are 50mm, and length is 100mm.
Take by weighing 17g γ-Al
2O
3, 2gCeO
2, 1g La
2O
3, 0.5g ZrO
2, mix back ball milling 5h; Other gets 1gH
2PtCl
66H
2O in 400 ℃ of following roasting 2h, obtains PtO in Muffle furnace
2Powder is got 0.5g PtO
2Powder joins in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mixes back ball milling 5h; Add water 55g, stir, and add pH value to 3～4 that an amount of nitric acid is regulated slurries, ball milling 12h makes catalyst-coated liquid again.
Metal beehive carrier is placed catalyst-coated liquid 5min, take out then, with vacuum suction device unnecessary coating liquid in the carrier is removed, dry 30min down for 200 ℃, 400 ℃ of following roasting 30min, insulation 30min, repetitive coatings-oven dry-roasting process 2 times, at last carrier is carried 550 ℃ of following roasting 5h, and insulation 12h.
Make catalyst cartridge by this prescription and be called A.
Embodiment two:
The hole density of metal beehive carrier: 300 orders, wall thickness 0.1mm, diameter are 150mm, length is 300mm;
Take by weighing 17g γ-Al
2O
3, 2.2gCeO
2, 0.86gLa
2O
3, 0.6gZrO
2And 0.059gY
2O
3, mix back ball milling 5h; Other gets 1gH
2PtCl
66H
2O in 400 ℃ of following roasting 2h, obtains PtO in Muffle furnace
2Powder is got 0.5g PtO
2Powder joins in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mixes back ball milling 5h; Add water 65g and stir, and add pH value that an amount of nitric acid regulates slurries to 3-4, ball milling 12h makes catalyst-coated liquid again.
Metal beehive carrier is placed catalyst-coated liquid 5min, take out then, with vacuum suction device unnecessary coating liquid in the carrier is removed, dry 30min down for 200 ℃, 400 ℃ of following roasting 30min, insulation 30min repeats coating procedure 1-2 time, at last carrier is carried 550 ℃ of following roasting 5h, and insulation 12h.
Make catalyst cartridge by this prescription and be called B.
Catalyst activity detects:
Unstripped gas source: gasoline engine exhaust
When α=1, catalytic reactor inlet temperature are that 280 ℃ and air speed are 9.5 * 10
4h
-1The time, catalyst is as shown in the table to the conversion ratio of the CO in the gasoline engine tail gas, HC and NOx:
| Catalyst | Temperature is that 280 ℃, air speed are 9.5 * 10 4h -1And the conversion ratio (%) of α=1 o'clock | ||
| ????CO | ????HC | ????NOx | |
| ????A | ????97.6 | ????90.2 | ????85 |
| ????B | ????95.1 | ????87 | ????83.2 |
Catalyst A, B are detected its activity behind the roasting 10h in air under 950 ℃ of high temperature
| Catalyst | Temperature is that 280 ℃, air speed are 9.5 * 10 4h -1And the conversion ratio (%) of α=1 o'clock | ||
| ????CO | ????HC | ????NOx | |
| ????A | ????95.4 | ????87.9 | ????80.6 |
| ????B | ????93.7 | ????84.8 | ????81.0 |
Annotate: α is a coefficient of excess air
When α changed near 1, catalyst A, B still showed advantages of high catalytic activity to CO, HC, NOx in addition, but the action pane that catalyst A, B be described still is a broad.
By the result of above-mentioned example, the catalyst low-temperature activity that this preparation method developed is good, still keeps advantages of high catalytic activity and stability under high-temperature roasting, shows triple effect activity preferably.
Embodiment three:
Select nickel chromium stainless steel honeycomb metallic carrier for use, hole density is 200 orders, and wall thickness 0.1mm, diameter are 35mm, and length is 50mm.
Take by weighing 17g γ-Al
2O
3, 2gCeO
2, 1gLa
2O
3Mix back ball milling 7h; Other gets 1.5gH
2PtCl
66H
2O in 400 ℃ of following roasting 2h, obtains PtO in Muffle furnace
2Powder is got 0.5g PtO
2Powder joins in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mixes back ball milling 6h; Add water 60g, stir, and add pH value that an amount of nitric acid regulates slurries to 3-4, ball milling 15h makes catalyst-coated liquid again.
Metal beehive carrier is placed catalyst-coated liquid 10min, take out then, with vacuum suction device unnecessary coating liquid in the carrier is removed, dry 30min down for 200 ℃, 400 ℃ of following roasting 40min, insulation 40min, repetitive coatings-oven dry-roasting process 2 times, at last carrier is carried 650 ℃ of following roasting 2h, and insulation 8h.
Embodiment four
Selecting for use of nickel chromium stainless steel honeycomb metallic carrier with embodiment three.
Take by weighing 17g Al
2O
3, 2gCeO
2, 1g La
2O
3, 0.5gZrO
2, mix back ball milling 5h; Other gets 1gH
2PtCl
66H
2O in 400 ℃ of following roasting 2h, obtains PtO in Muffle furnace
2Powder is got 0.25g PtO
2Powder joins in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mixes back ball milling 5h; Add water 55g, stir, and add pH value that an amount of nitric acid regulates slurries to 3-4, ball milling 12h makes catalyst-coated liquid again.
Metal beehive carrier is placed catalyst-coated liquid 5min, take out then, with vacuum suction device unnecessary coating liquid in the carrier is removed, dry 30min down for 200 ℃, 400 ℃ of following roasting 20min, insulation 20min, repetitive coatings-oven dry-roasting process 1 time, at last carrier is carried 400 ℃ of following roasting 3h, and insulation 9h.
Embodiment five:
Selecting for use of nickel chromium stainless steel honeycomb metallic carrier with embodiment three.
Take by weighing 17g γ-Al
2O
3, 2gCeO
2, 1gLa
2O
3Mix back ball milling 5h; Other gets 1.5g PdCl
2, in Muffle furnace,, obtain the PdO powder in 400 ℃ of following roasting 2h, get the 0.5gPdO powder and join in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mix back ball milling 5h; Add water 65g, stir, and add pH value that an amount of nitric acid regulates slurries to 3-4, ball milling 12h makes catalyst-coated liquid again.
Metal beehive carrier is placed catalyst-coated liquid 5min, take out then, with vacuum suction device unnecessary coating liquid in the carrier is removed, dry 30min down for 200 ℃, 400 ℃ of following roasting 30min, insulation 30min, repetitive coatings-oven dry-roasting process 3 times, at last carrier is carried 550 ℃ of following roasting 5h, and insulation 12h.
Embodiment six:
Selecting for use of nickel chromium stainless steel honeycomb metallic carrier with embodiment three.
Take by weighing 17g γ-Al
2O
3, 2gCeO
2, 1g La
2O
3, 0.5gZrO
2Ball milling 5h; Other gets 1g PdCl
2, in Muffle furnace,, obtain the PdO powder in 400 ℃ of following roasting 2h, get the 0.2gPdO powder and join in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mix back ball milling 5h; Add water 65g, stir, and add pH value to 3～4 that an amount of nitric acid is regulated slurries, ball milling 12h makes catalyst-coated liquid again.
Other technology is with embodiment two.
Embodiment seven:
Selecting for use of nickel chromium stainless steel honeycomb metallic carrier with embodiment three.
Take by weighing 17g γ-Al
2O
3, 2gCeO
2, 1g La
2O
3, 0.5gZrO
2, mix back ball milling 5h; Get 1gH in addition respectively
2PtCl
66H
2O, 1g PdCl
2, in Muffle furnace,, obtain PtO in 400 ℃ of following roasting 2h
2, the PdO powder, get 0.4g PtO
2, 0.2g PdO powder joins in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mixes back ball milling 5h; Add water 55g, stir, and add pH value to 3～4 that an amount of nitric acid is regulated slurries, ball milling 12h makes catalyst-coated liquid again.
Other technology is with embodiment two.
Embodiment eight:
Selecting for use of nickel chromium stainless steel honeycomb metallic carrier with embodiment three.
Take by weighing 17g γ-Al
2O
3, 2gCeO
2, 1g La
2O
3, 0.5gZrO
2, 0.1gY
2O
3, mix back ball milling 5h; Get 1gH in addition respectively
2PtCl
66H
2O, 1g PdCl
2, in Muffle furnace,, obtain PtO in 400 ℃ of following roasting 2h
2, the PdO powder, get 0.4g PtO
2, 0.2g PdO powder joins in the active oxidation aluminium powder that ball milling crosses (containing auxiliary agent), mixes back ball milling 4h; Add water 55g, stir, and add pH value that an amount of nitric acid regulates slurries to 3-4, ball milling 10h makes catalyst-coated liquid again.
Other technology is with embodiment two.
Claims (5)
1, the preparation method of metallic honeycomb substrate catalyst may further comprise the steps:
A, processing: the nickel chromium stainless steel honeycomb carries out preliminary treatment as first carrier to this metal beehive carrier, promptly under 300～400 ℃ of temperature conditions roasting 1-3 hour;
B, preparation powdered form catalyst: the active oxidation aluminium powder that auxiliary agent, active constituent are added as second carrier is γ-Al successively
2O
3In carry out ball milling, make the powdered form catalyst:
At first, add the auxiliary agent that accounts for active oxidation aluminium powder gross weight 10-20%, ball milling 3-7 hour, wherein auxiliary agent is chosen and contained cerium oxide and lanthana, both weight ratio cerium oxide: lanthana was (1.6～3): (0.4～1);
Secondly, add the active constituent that accounts for active oxidation aluminium powder gross weight 1-4%, ball milling 3-7 hour, wherein active constituent is platinum oxide or palladium oxide or both by platinum oxide: palladium oxide was (2-3): the combination of 1 weight ratio;
At last, obtain the thinner powdered form catalyst that contains auxiliary agent of granularity;
C, preparation coating liquid: with above-mentioned powdered form catalyst and water by being 1: weight ratio (2-3.5) is mixed, fully stirs to make it to mix, and the interpolation small amount of acid, and the pH value of controlling slurries is 3-4;
With the slurries that make ball milling 8-15 hour again, make catalyst-coated liquid;
D, coating: with the dipping mode to the metal beehive carrier hanging, after hanging finishes coating liquid unnecessary in the metal beehive carrier is removed, subsequently the evenly oven dry under 100-300 ℃ of temperature of coated metal beehive carrier, time is 20-40min, then metal beehive carrier is put into Muffle furnace in 300-500 ℃ of roasting temperature 20-40min, and insulation 20-40min;
Once more to metal beehive carrier apply, oven dry, roasting, repeat at least 1-2 time;
E, roasting: the metal beehive carrier that will be loaded with catalyst-coated liquid at last places Muffle furnace in 350-650 ℃ of following roasting 2-7h, and insulation 8-15h.
2, preparation method according to claim 1, also contain in zirconia, the yittrium oxide one or both in the described auxiliary agent, and the proportionate relationship of cerium oxide, lanthana: cerium oxide: lanthana: zirconia: yittrium oxide is (1.6～3): (0.4～1): (0～1): (0～0.1).
3, preparation method according to claim 1, platinum oxide and palladium oxide are to make by roasting chloroplatinic acid, palladium bichloride in the described active constituent.
4, preparation method according to claim 1 regulates the pH value and adopts nitric acid.
5, preparation method according to claim 1, described aluminium oxide is an activated alumina, its molecular formula is γ-Al
2O
3
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