CN108499569A - The multi-metal oxide catalyst and preparation method thereof of diesel emission particulate is removed for low temperature - Google Patents
The multi-metal oxide catalyst and preparation method thereof of diesel emission particulate is removed for low temperature Download PDFInfo
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- CN108499569A CN108499569A CN201810260815.1A CN201810260815A CN108499569A CN 108499569 A CN108499569 A CN 108499569A CN 201810260815 A CN201810260815 A CN 201810260815A CN 108499569 A CN108499569 A CN 108499569A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
- F01N3/0231—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using special exhaust apparatus upstream of the filter for producing nitrogen dioxide, e.g. for continuous filter regeneration systems [CRT]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
A kind of multi-metal oxide catalyst for removing diesel emission particulate under low temperature belongs to diesel engine vent gas exhaust pollutant control technical field.The present invention uses ZrO2For matrix, with CuO, CeO2For main active component.ZrO2, CuO, CeO2Molar percentage be respectively：10%~45%, 10%~90%, 10%~45%.Specifically catalyst preparation process includes：Determination, the configuration of catalyst precursor combustion fluid, load of the catalyst on DPF cordierite carriers of metal oxide matrix and main active constituent load capacity.The present invention replaces Ce using the parts Cu of high oxidative, to the CO of catalyst low-temperature catalytic oxidation activity and catalyst2Selectivity has a more substantial increase, and carbon soot particles are efficiently removed in 150~400 DEG C of exhaust emissions of diesel engine temperature range, which has stronger anti-sulfur poisonous performance, is suitable for the high-sulfur diesel oil in China and urban road traffic status.
Description
Technical field
The present invention relates to a kind of multi-metal oxide catalysts removing diesel emission particulate for low temperature, especially
One kind containing ZrO2、CuO、CeO2, there are the more of excellent (350~400 DEG C) removal diesel emission particulate performances at low temperature
First metal oxide catalyst belongs to diesel engine vent gas solid pollutant control technology field.
Background technology
DPF soot filtering techniques be considered as under current technical conditions diesel vehicle soot particle remove divided by reach maximum discharge mark
Accurate best-of-breed technology means, DPF carriers regenerate after carbon soot particles are carried out with physics trapping.It is catalyzed using being added
The passive regeneration system that agent obtains, i.e. continuous oxidation regenerative system can enable soot at diesel engine vent gas temperature (150-400 DEG C)
Under the conditions of realize the regeneration of continuous active.
C+O2→CO(CO2)
C+NO2→CO(CO2)+NO
Noble metal catalyst, can be by NO efficient oxidations at NO2, promote particle and NO2Oxidation reaction realizes good carbon
Particle oxidation catalysis effect.But the higher operating costs of noble metal, and in practical applications, need at lower temperatures, i.e.,
It is realized than more preferably carbon particle oxidation catalysis effect in diesel engine vent gas temperature range (150-400 DEG C).
The study found that ZrO2In Zr4+The activity of catalyst carbon oxide particle can not only be improved, additionally it is possible to significantly carry
The thermal stability and repeatability of high catalyst extend the service life of catalyst and DPF carriers.In ZrO2Middle addition Ce can be significantly
Carbon particle oxidation activity is promoted, cerium oxide itself has preferable oxygen migration, storge quality and thermal stability, Ce4+And Ce3+Tool
There is good redox ability.CeZrOxCatalyst has very high combustion activity at 450 DEG C.
Cu in CuO catalyst2+There is high migration, research shows that Cu2+It can act synergistically with Ce, by CeZrOxIt urges
Ce in agent can further increase oxygen migration, storage and release performance with the substitution of the parts Cu, improve the oxidation of catalyst also
Originality energy, contributes to particle burning.In addition the high oxidative of Cu can also improve the selectivity of reaction, mitigate the generation of CO with
Secondary pollution caused by discharge.Therefore, the combination that the invention passes through active constituent Cu, Ce (higher low temperature active and selectivity)
The multi-metal oxide catalyst of diesel emission particulate is efficiently removed under exploitation low temperature.
Invention content
The technical problem to be solved by the present invention is to overcome previous non-precious metal catalyst low temperature (<450 DEG C) under the conditions of
Activity is relatively low, the poor defect of selectivity.
For the different temperatures characteristic of various metal oxide oxidation catalyst activity and selectivities, according to the principle of mutual supplement with each other's advantages,
It is studied through test of many times, research and design is suitable for the CuCeZrO of the low temperature of diesel vehicle DPF system/highly selectivexMulti-element metal
Oxide catalyst.The catalyst have adapt to reaction temperature be in 150~400 DEG C of diesel exhaust gas temperature range compared with
The features such as high catalytic activity and preferable selectivity.
The present invention is achieved through the following technical solutions, and the present invention includes a kind of multi-metal oxide catalyst,
Its matrix component is ZrO2, active component CuO, CeO2。
Further, in the present invention, matrix component ZrO2With active component CuO, CeO2Element molar percentage be：
ZrO2(5%~45%), CuO (10%~90%), CeO2(5%~45%), the sum of molar percentage are 100%.
Further, in the present invention, ZrO2Presoma be five water zirconium nitrates, the presoma of CuO is nitrate trihydrate
Copper, CeO2Presoma be cerium nitrate hexahydrate.
Further, in the present invention, its specific surface area of finished catalyst obtained is in 70-90m2Between/g.
The present invention is in existing less toxic rare earth metal ZrCeOxHigh oxidation activity gold is introduced on the basis of oxide catalyst
Belong to element Cu and carrys out partial alternative Ce collectively as active constituent.On catalyst performance, since the valence electron of Ce elements can be not
With phase co-conversion between valence state, to show CeO2、Ce2O3、Ce2O5Etc. different oxide types, in reaction temperature and reactant
Under the action of component, different oxides can be converted mutually, and the free oxygen and free electron of generation can further promote catalysis anti-
The progress answered；In addition, be added mainly in the form of CuO existing for Cu oxides, be capable of providing catalysis reaction active sites, promote oxygen
The absorption of gas and NO, and reacted, generate the NO of strong oxidizing property2, further aoxidize soot.In addition, such oxo transition metal
The addition of compound can also increase the electronics transfer in catalysis reaction, as preferable storage oxygen agent, enhance the oxygen of catalyst
Recoverability.
The invention also includes a kind of sides preparing multi-metal oxide catalyst by SHS self-propagating high-temperature flame combustion process
Method, specific method include the following steps：
First, the determination of metal oxide matrix and main active constituent load capacity：
According to catalyst matrix component ZrO described in claims 22Molar percentage 5%~45%, active component CuO
Molar percentage be 10%~90%, CeO2Molar percentage be 5%~45%, respectively according to five water nitre of every 429.32g
Sour zirconium generates 122.98g ZrO2, 204.116g CeO are generated per 434.22g cerium nitrate hexahydrates2, per 187.56g nitrate trihydrate copper
Generate 79.5g CuO ratiometric conversion go out five water zirconium nitrates of required experimental drug, cerium nitrate hexahydrate, nitrate trihydrate copper matter
Amount；
Second, the configuration of catalyst precursor combustion fluid：
Presoma combustion fluid is configured according to the calculated quality of step 1；Weigh five water zirconium nitrates, cerium nitrate hexahydrate, three water
Copper nitrate is dissolved in 500ml ionized waters, and glycine is added and adjusts solution pH value；It dissolves by heating under 60 DEG C of constant temperature, and is stirred in magnetic force
It mixes to stir on machine and obtains within one hour uniformly clear presoma combustion fluid；
Third, coating of the catalyst on DPF cordierite carriers：
According to the presoma combustion fluid that step 2 configures DPF is coated in using SHS self-propagating high-temperature flame combustion process
On carrier；DPF carriers are immersed into 1min in above-mentioned presoma combustion fluid, empty the air in channel, making solution, its is full and uniform
It is distributed on honeycomb substrate wall surface；DPF sample carriers after immersion are picked up with tweezers, are stood in the crucible of 100ml specifications, it will
Crucible is put into the conflagration synthesis that catalyst is carried out in Muffle furnace (furnace temperature is adjusted to 350 DEG C of preheating 1h in advance) with crucible tongs
8min；Hereafter crucible is taken out from Muffle furnace, carrier is enabled to be quickly cooled down 1min in air；Repeat above-mentioned dipping, burned
Journey, until reaching the expection coated weight of catalyst；The DPF carriers for being up to catalyst coated weight are put into 450 DEG C of Muffle furnaces and roast
5h is burnt, the coating strong degree of catalyst is reinforced.
Compared with prior art, the present invention have the advantages that for：
First, CuCeZrOx multi-metal oxide catalysts of the invention have higher low-temperature catalytic oxidation performance,
Especially in diesel exhaust gas temperature range (150~400 DEG C), the regeneration efficiency of DPF is increased substantially, is utilized to reach
The multicomponent catalyst realizes the continuous active in 100~400 DEG C of warm temperature ranges of diesel engine row and is regenerated to DPF carriers,
Especially suitable for China's urban road passage condition；
Second, catalyst of the invention not only at a lower temperature (150~400 DEG C) there is high activity, stability, and it is simultaneous
CO is cared for2Generate selectivity, it is therefore prevented that a large amount of generations of polluted gas CO；
Third, some transition metal elements make that apparent synergism can be played in catalyst, not only such as the addition of Ce
Be conducive to raising and stably catalyzed performance, while inhibited to the side effect of sulfur dioxide present in tail gas.It is added
A certain amount of SO2Catalyst activity is had little effect.
4th, catalyst of the invention selects the oxide of common metal zirconium, copper, cerium as component, and it is cheap to prepare raw material
It is easy to get, catalyst preparation process is simple, non-toxic, harmless and pollution-free, easy to operate.
Description of the drawings
Fig. 1 is the structure for the soot device for evaluating performance of removal diesel engine DPF loads for catalyst of the invention
Schematic diagram；
Wherein：1、NO/N2Diluent gas bottle, 2, O2/N2Diluent gas bottle, 3, high-purity N2Bottle, 4, mass flow controller,
5, manual ball valve, 6, DPF quartz tube reactors, 7, the carrier of supported catalyst and soot, 8, temperature display controller, 9, return
Rotatable tube type resistance furnace, 10, Fourier Transform Infrared Spectrometer.
Specific implementation mode
It elaborates below in conjunction with the accompanying drawings to the embodiment of the present invention, before the present embodiment is with technical solution of the present invention
It carries, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Case study on implementation
As shown in Figure 1, the evaluating apparatus of the present invention includes NO/N2Diluent gas bottle 1, O2/N2Diluent gas bottle 2, high-purity N2
Bottle 3, mass flow controller 4, manual ball valve 5, DPF quartz tube reactors 6, supported catalyst and the carrier 7 of soot, temperature
Display controller 8, swinging tube type resistance furnace 9, Fourier Transform Infrared Spectrometer 10, NO/N2Diluent gas bottle 1, O2/N2It is dilute
Release gas bottle 2, high-purity N2Manual ball valve 5 and mass flow controller 4 be installed respectively on the gas exhaust piping of bottle 3, in three gas cylinders
Gas mixing after be passed through DPF quartz tube reactors 6, the carrier 7 of supported catalyst and soot is arranged in quartz tube reactor 6
Interior, swinging tube type resistance furnace 9 is arranged in the periphery of quartz tube reactor 6, temperature display controller 8 and swinging tubular electric resistance
Stove 9 is connected, and Fourier Transform Infrared Spectrometer 10 is arranged in the tail portion of quartz tube reactor 6.
In the present invention, the carrier after load carbon soot particles is placed in catalyst fixed bed reactor, and has diesel engine mould
Quasi- tail gas passes through, and in atmospheric conditions, reaction temperature is 100 to 650 DEG C so that 90% to 100% ground of soot of load is gone
It removes, diesel engine simulated exhaust gas space velocity range is：5000 to 30000h-1, volume concentration range shared by diesel engine simulated exhaust gas oxygen
For：5% to 10%, NO in diesel engine simulated exhaust gasxShared volumetric concentration is：600 to 1000ppm.
Embodiment 1
(1) determination of metal oxide matrix and main active constituent load capacity
According to ZrO2:CeO2:CuO=45:45：10 molar ratio be calculated catalyst load drug dosage be respectively：
Five water zirconium nitrate 19.3g, cerium nitrate hexahydrate 19.5g, nitrate trihydrate copper 2.41g.
(2) catalyst precursor combustion fluid configures
Presoma combustion fluid is configured according to the calculated quality of step (1).Weigh five water zirconium nitrate 19.3g, six water nitric acid
Cerium 19.5g, nitrate trihydrate copper 2.41g are dissolved in 500ml ionized waters, and glycine 13.9g is added and adjusts solution pH value.In 60 DEG C of constant temperature
Lower heating for dissolving, and stirred on magnetic stirrer and obtain within one hour uniformly clear presoma combustion fluid.
(3) coating of the catalyst on DPF cordierite carriers
The presoma combustion fluid obtained according to step (2) configuration is coated in DPF using SHS self-propagating high-temperature flame combustion process
On carrier.DPF carriers are immersed into 1min in above-mentioned presoma combustion fluid, empty the air in channel, making solution, its is full and uniform
It is distributed on honeycomb substrate wall surface.DPF sample carriers after immersion are picked up with tweezers, are stood in the crucible of 100ml specifications, it will
Crucible is put into the conflagration synthesis that catalyst is carried out in Muffle furnace (furnace temperature is adjusted to 350 DEG C of preheating 1h in advance) with crucible tongs
8min.Hereafter crucible is taken out from Muffle furnace, carrier is enabled to be quickly cooled down 1min in air；Repeat above-mentioned dipping, burned
Journey, until reaching the expection coated weight of catalyst.The DPF carriers for being up to catalyst coated weight are put into 450 DEG C of Muffle furnaces and roast
5h is burnt, the coating strong degree of catalyst is reinforced.
Catalyst obtained in embodiment 1 is known as catalyst A.
(4) carbon particle load, DPF samples are carried out to the DPF carriers after coating catalyst using small-sized PM quick loading devices
The soot loading capacity of product carrier is 6g/L (being 4~6g/L on diesel engine particles supplementary set device), and loading carbon particle used is
Printex-U, grain size 25nm, specific surface area 100m2/g.The determination of PM loading capacities is to load front and back DPF samples by weighing
Product carrier quality is poor.
Catalyst A is evaluated in NH with the soot device for evaluating performance of removal diesel engine DPF loads shown in FIG. 13- SCR is anti-
Catalytic performance in answering.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 800ppm, the volumetric concentration of oxygen
It is 6.5%, reaction temperature is 100~650 DEG C, air speed 30000h-1。NO、NO2、CO、CO2With Fourier transform infrared light
Spectrometer and its gas cell attachment measure.At a temperature of differential responses (100~650 DEG C) catalyst oxidation soot efficiency and
CO2Selectivity is shown in Tables 1 and 2 respectively.
Embodiment 2
(1) determination of metal oxide matrix and main active constituent load capacity
According to ZrO2:CeO2:CuO=40:40：20 molar ratio be calculated catalyst load drug dosage be respectively：
Five water zirconium nitrate 17.1g, cerium nitrate hexahydrate 17.3g, nitrate trihydrate copper 9.6g.
(2) catalyst precursor combustion fluid configures
Presoma combustion fluid is configured according to the calculated quality of step (1).Weigh five water zirconium nitrate 17.1g, six water nitric acid
Cerium 17.3g, nitrate trihydrate copper 9.6g are dissolved in 500ml ionized waters, and glycine 13.3g is added and adjusts solution pH value.In 60 DEG C of constant temperature
Lower heating for dissolving, and stirred on magnetic stirrer and obtain within one hour uniformly clear presoma combustion fluid.
(3) coating of the catalyst on DPF cordierite carriers
The presoma combustion fluid obtained according to step (2) configuration is coated in DPF using SHS self-propagating high-temperature flame combustion process
On carrier.DPF carriers are immersed into 1min in above-mentioned presoma combustion fluid, empty the air in channel, making solution, its is full and uniform
It is distributed on honeycomb substrate wall surface.DPF sample carriers after immersion are picked up with tweezers, are stood in the crucible of 100ml specifications, it will
Crucible is put into the conflagration synthesis that catalyst is carried out in Muffle furnace (furnace temperature is adjusted to 350 DEG C of preheating 1h in advance) with crucible tongs
8min.Hereafter crucible is taken out from Muffle furnace, carrier is enabled to be quickly cooled down 1min in air；Repeat above-mentioned dipping, burned
Journey, until reaching the expection coated weight of catalyst.The DPF carriers for being up to catalyst coated weight are put into 450 DEG C of Muffle furnaces and roast
5h is burnt, the coating strong degree of catalyst is reinforced.
Catalyst obtained in embodiment 2 is known as catalyst B.
(4) carbon particle load, DPF samples are carried out to the DPF carriers after coating catalyst using small-sized PM quick loading devices
The soot loading capacity of product carrier is 6g/L (being 4~6g/L on diesel engine particles supplementary set device), and loading carbon particle used is
Printex-U, grain size 25nm, specific surface area 100m2/g.The determination of PM loading capacities is to load front and back DPF samples by weighing
Product carrier quality is poor.
Catalyst B is evaluated in NH with the soot device for evaluating performance of removal diesel engine DPF loads shown in FIG. 13- SCR is anti-
Catalytic performance in answering.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 800ppm, the volumetric concentration of oxygen
It is 6.5%, reaction temperature is 100~650 DEG C, air speed 30000h-1。NO、NO2、CO、CO2With Fourier transform infrared light
Spectrometer and its gas cell attachment measure.At a temperature of differential responses (100~650 DEG C) catalyst oxidation soot efficiency and
CO2Selectivity is shown in Tables 1 and 2 respectively.
Embodiment 3
(1) determination of metal oxide matrix and main active constituent load capacity
According to ZrO2:CeO2:CuO=25:25：50 molar ratio be calculated catalyst load drug dosage be respectively：
Five water zirconium nitrate 10.7g, cerium nitrate hexahydrate 10.8g, nitrate trihydrate copper 12.1g.
(2) catalyst precursor combustion fluid configures
Presoma combustion fluid is configured according to the calculated quality of step (1).Weigh five water zirconium nitrate 10.7g, six water nitric acid
Cerium 10.8g, nitrate trihydrate copper 12.1g are dissolved in 500ml ionized waters, and glycine 11.4g is added and adjusts solution pH value.In 60 DEG C of constant temperature
Lower heating for dissolving, and stirred on magnetic stirrer and obtain within one hour uniformly clear presoma combustion fluid.
(3) coating of the catalyst on DPF cordierite carriers
The presoma combustion fluid obtained according to step (2) configuration is coated in DPF using SHS self-propagating high-temperature flame combustion process
On carrier.DPF carriers are immersed into 1min in above-mentioned presoma combustion fluid, empty the air in channel, making solution, its is full and uniform
It is distributed on honeycomb substrate wall surface.DPF sample carriers after immersion are picked up with tweezers, are stood in the crucible of 100ml specifications, it will
Crucible is put into the conflagration synthesis that catalyst is carried out in Muffle furnace (furnace temperature is adjusted to 350 DEG C of preheating 1h in advance) with crucible tongs
8min.Hereafter crucible is taken out from Muffle furnace, carrier is enabled to be quickly cooled down 1min in air；Repeat above-mentioned dipping, burned
Journey, until reaching the expection coated weight of catalyst.The DPF carriers for being up to catalyst coated weight are put into 450 DEG C of Muffle furnaces and roast
5h is burnt, the coating strong degree of catalyst is reinforced.
Catalyst obtained in embodiment 3 is known as catalyst C.
(4) carbon particle load, DPF samples are carried out to the DPF carriers after coating catalyst using small-sized PM quick loading devices
The soot loading capacity of product carrier is 6g/L (being 4~6g/L on diesel engine particles supplementary set device), and loading carbon particle used is
Printex-U, grain size 25nm, specific surface area 100m2/g.The determination of PM loading capacities is to load front and back DPF samples by weighing
Product carrier quality is poor.
Catalyst C is evaluated in NH with the soot device for evaluating performance of removal diesel engine DPF loads shown in FIG. 13- SCR is anti-
Catalytic performance in answering.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 800ppm, the volumetric concentration of oxygen
It is 6.5%, reaction temperature is 100~650 DEG C, air speed 30000h-1。NO、NO2、CO、CO2With Fourier transform infrared light
Spectrometer and its gas cell attachment measure.At a temperature of differential responses (100~650 DEG C) catalyst oxidation soot efficiency and
CO2Selectivity is shown in Tables 1 and 2 respectively.
Embodiment 4
(1) determination of metal oxide matrix and main active constituent load capacity
According to ZrO2:CeO2:CuO=15:15：70 molar ratio be calculated catalyst load drug dosage be respectively：
Five water zirconium nitrate 6.4g, cerium nitrate hexahydrate 6.5g, nitrate trihydrate copper 16.9g.
(2) catalyst precursor combustion fluid configures
Presoma combustion fluid is configured according to the calculated quality of step (1).Weigh five water zirconium nitrate 6.4g, cerium nitrate hexahydrate
6.5g, nitrate trihydrate copper 16.9g are dissolved in 500ml ionized waters, and glycine 10.2g is added and adjusts solution pH value.Under 60 DEG C of constant temperature
It dissolves by heating, and is stirred on magnetic stirrer and obtain within one hour uniformly clear presoma combustion fluid.
(3) coating of the catalyst on DPF cordierite carriers
The presoma combustion fluid obtained according to step (2) configuration is coated in DPF using SHS self-propagating high-temperature flame combustion process
On carrier.DPF carriers are immersed into 1min in above-mentioned presoma combustion fluid, empty the air in channel, making solution, its is full and uniform
It is distributed on honeycomb substrate wall surface.DPF sample carriers after immersion are picked up with tweezers, are stood in the crucible of 100ml specifications, it will
Crucible is put into the conflagration synthesis that catalyst is carried out in Muffle furnace (furnace temperature is adjusted to 350 DEG C of preheating 1h in advance) with crucible tongs
8min.Hereafter crucible is taken out from Muffle furnace, carrier is enabled to be quickly cooled down 1min in air；Repeat above-mentioned dipping, burned
Journey, until reaching the expection coated weight of catalyst.The DPF carriers for being up to catalyst coated weight are put into 450 DEG C of Muffle furnaces and roast
5h is burnt, the coating strong degree of catalyst is reinforced.
Catalyst obtained in embodiment 4 is known as catalyst D.
(4) carbon particle load, DPF samples are carried out to the DPF carriers after coating catalyst using small-sized PM quick loading devices
The soot loading capacity of product carrier is 6g/L (being 4~6g/L on diesel engine particles supplementary set device), and loading carbon particle used is
Printex-U, grain size 25nm, specific surface area 100m2/g.The determination of PM loading capacities is to load front and back DPF samples by weighing
Product carrier quality is poor.
Catalyst D is evaluated in NH with the soot device for evaluating performance of removal diesel engine DPF loads shown in FIG. 13- SCR is anti-
Catalytic performance in answering.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 800ppm, the volumetric concentration of oxygen
It is 6.5%, reaction temperature is 100~650 DEG C, air speed 30000h-1。NO、NO2、CO、CO2With Fourier transform infrared light
Spectrometer and its gas cell attachment measure.At a temperature of differential responses (100~650 DEG C) catalyst oxidation soot efficiency and
CO2Selectivity is shown in Tables 1 and 2 respectively.
Embodiment 5
(1) determination of metal oxide matrix and main active constituent load capacity
According to ZrO2:CeO2:CuO=10:10：90 molar ratio be calculated catalyst load drug dosage be respectively：
Five water zirconium nitrate 2.15g, cerium nitrate hexahydrate 2.17g, nitrate trihydrate copper 21.7g.
(2) catalyst precursor combustion fluid configures
Presoma combustion fluid is configured according to the calculated quality of step (1).Weigh five water zirconium nitrate 2.15g, six water nitric acid
Cerium 2.17g, nitrate trihydrate copper 21.7g are dissolved in 500ml ionized waters, and glycine 8.96g is added and adjusts solution pH value.In 60 DEG C of constant temperature
Lower heating for dissolving, and stirred on magnetic stirrer and obtain within one hour uniformly clear presoma combustion fluid.
(100~650 DEG C) catalyst soot efficiency activity evaluation result at a temperature of 1 differential responses of table
(100~650 DEG C) catalyst aoxidizes CO at a temperature of 2 differential responses of table2Selective evaluation result
(3) coating of the catalyst on DPF cordierite carriers
The presoma combustion fluid obtained according to step (2) configuration is coated in DPF using SHS self-propagating high-temperature flame combustion process
On carrier.DPF carriers are immersed into 1min in above-mentioned presoma combustion fluid, empty the air in channel, making solution, its is full and uniform
It is distributed on honeycomb substrate wall surface.DPF sample carriers after immersion are picked up with tweezers, are stood in the crucible of 100ml specifications, it will
Crucible is put into the conflagration synthesis that catalyst is carried out in Muffle furnace (furnace temperature is adjusted to 350 DEG C of preheating 1h in advance) with crucible tongs
8min.Hereafter crucible is taken out from Muffle furnace, carrier is enabled to be quickly cooled down 1min in air；Repeat above-mentioned dipping, burned
Journey, until reaching the expection coated weight of catalyst.The DPF carriers for being up to catalyst coated weight are put into 450 DEG C of Muffle furnaces and roast
5h is burnt, the coating strong degree of catalyst is reinforced.
Catalyst obtained in embodiment 5 is known as catalyst E.
(4) carbon particle load, DPF samples are carried out to the DPF carriers after coating catalyst using small-sized PM quick loading devices
The soot loading capacity of product carrier is 6g/L (being 4~6g/L on diesel engine particles supplementary set device), and loading carbon particle used is
Printex-U, grain size 25nm, specific surface area 100m2/g.The determination of PM loading capacities is to load front and back DPF samples by weighing
Product carrier quality is poor.
Catalyst E is evaluated in NH with the soot device for evaluating performance of removal diesel engine DPF loads shown in FIG. 13- SCR is anti-
Catalytic performance in answering.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 800ppm, the volumetric concentration of oxygen
It is 6.5%, reaction temperature is 100~650 DEG C, air speed 30000h-1。NO、NO2、CO、CO2With Fourier transform infrared light
Spectrometer and its gas cell attachment measure.At a temperature of differential responses (100~650 DEG C) catalyst oxidation soot efficiency and
CO2Selectivity is shown in Tables 1 and 2 respectively.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (5)
1. a kind of multi-metal oxide catalyst for low temperature removal diesel emission particulate, which is characterized in that matrix group
It is divided into ZrO2, active component CuO, CeO2。
2. the multi-metal oxide catalyst according to claim 1, for low temperature removal diesel emission particulate,
It is characterized in that described matrix component ZrO2With active component CuO, CeO2Element molar percentage be：ZrO2(5%~
45%), CuO (10%~90%), CeO2(5%~45%), the sum of molar percentage are 100%.
3. the multi-metal oxide catalyst according to claim 2, for low temperature removal diesel emission particulate,
It is characterized in that ZrO2Presoma be five water zirconium nitrates, the presoma of CuO is nitrate trihydrate copper, CeO2Presoma be six water
Cerous nitrate.
4. the multi-metal oxide catalyst according to claim 3, for low temperature removal diesel emission particulate,
It is characterized in that its specific surface area of finished catalyst obtained is in 70-90m2Between/g.
5. a kind of preparation method of catalyst as claimed in claim 1, it is characterised in that preparation method is SHS high temperature from climing
Prolong flame combustion process, specifically includes following steps：
First, the determination of metal oxide matrix and main active constituent load capacity；According to catalyst matrix described in claims 2
Component ZrO2The molar percentage of molar percentage 5%~45%, active component CuO is 10%~90%, CeO2Mole percent
Than being 5%~45%, 122.98g ZrO are generated according to five water zirconium nitrates of every 429.32g respectively2, per 434.22g cerium nitrate hexahydrates
Generate 204.116g CeO2, the ratiometric conversion that 79.5g CuO are generated per 187.56g nitrate trihydrate copper goes out required experimental drug
The quality of five water zirconium nitrates, cerium nitrate hexahydrate, nitrate trihydrate copper；
Second, the configuration of catalyst precursor combustion fluid：
Presoma combustion fluid is configured according to the calculated quality of step 1；Weigh five water zirconium nitrates, cerium nitrate hexahydrate, nitrate trihydrate
Copper is dissolved in 500ml ionized waters, and glycine is added and adjusts solution pH value；It is dissolved by heating under 60 DEG C of constant temperature, and in magnetic stirrer
Upper stirring obtains uniformly clear presoma combustion fluid for one hour；
Third, coating of the catalyst on DPF cordierite carriers：
According to the presoma combustion fluid that step 2 configures DPF carriers are coated in using SHS self-propagating high-temperature flame combustion process
On；DPF carriers are immersed into 1min in above-mentioned presoma combustion fluid, the air in channel is emptied, makes its full and uniform distribution of solution
In on honeycomb substrate wall surface；DPF sample carriers after immersion are picked up with tweezers, are stood in the crucible of 100ml specifications, by crucible
The conflagration synthesis that catalyst is carried out in Muffle furnace (furnace temperature is adjusted to 350 DEG C of preheating 1h in advance) is put into crucible tongs
8min；Hereafter crucible is taken out from Muffle furnace, carrier is enabled to be quickly cooled down 1min in air；Repeat above-mentioned dipping, burned
Journey, until reaching the expection coated weight of catalyst；The DPF carriers for being up to catalyst coated weight are put into 450 DEG C of Muffle furnaces and roast
5h is burnt, the coating strong degree of catalyst is reinforced.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110107380A (en) * | 2019-04-17 | 2019-08-09 | 湖南冠拓科技股份有限公司 | A kind of diesel engine vent gas carbon particle collector removes carbon method and apparatus |
| CN110280265A (en) * | 2019-07-18 | 2019-09-27 | 付华 | A kind of multi-metal oxide catalyst and preparation method thereof for catalysis DPF passive regeneration under low temperature |
| CN111298644A (en) * | 2020-03-11 | 2020-06-19 | 安徽艾可蓝环保股份有限公司 | DPF high-temperature regeneration furnace and DPF high-temperature regeneration furnace exhaust purification method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101491778A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of thin shell shaped noble metal catalyst |
| CN106000414A (en) * | 2016-05-26 | 2016-10-12 | 上海交通大学 | Catalyst for removing NOx of diesel engine and preparation method thereof |
| CN106807385A (en) * | 2016-12-27 | 2017-06-09 | 中国科学院上海硅酸盐研究所 | A kind of soot combustion catalyst of nest like and its preparation method and application |
| CN106824173A (en) * | 2017-03-01 | 2017-06-13 | 石河子大学 | A kind of SCR catalyst for denitrating flue gas and preparation method thereof |
-
2018
- 2018-03-27 CN CN201810260815.1A patent/CN108499569A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101491778A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of thin shell shaped noble metal catalyst |
| CN106000414A (en) * | 2016-05-26 | 2016-10-12 | 上海交通大学 | Catalyst for removing NOx of diesel engine and preparation method thereof |
| CN106807385A (en) * | 2016-12-27 | 2017-06-09 | 中国科学院上海硅酸盐研究所 | A kind of soot combustion catalyst of nest like and its preparation method and application |
| CN106824173A (en) * | 2017-03-01 | 2017-06-13 | 石河子大学 | A kind of SCR catalyst for denitrating flue gas and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JAVIER GIMÉNEZ-MAÑOGIL ET AL: "Identifying the nature of the copper entities over ceria-based supports to promote diesel soot combustion: Synergistic effffects", 《APPLIED CATALYSIS A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110107380A (en) * | 2019-04-17 | 2019-08-09 | 湖南冠拓科技股份有限公司 | A kind of diesel engine vent gas carbon particle collector removes carbon method and apparatus |
| CN110280265A (en) * | 2019-07-18 | 2019-09-27 | 付华 | A kind of multi-metal oxide catalyst and preparation method thereof for catalysis DPF passive regeneration under low temperature |
| CN111298644A (en) * | 2020-03-11 | 2020-06-19 | 安徽艾可蓝环保股份有限公司 | DPF high-temperature regeneration furnace and DPF high-temperature regeneration furnace exhaust purification method |
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