CN101829579A - Preparation method and application of cerium-zirconium composite oxide catalyst loaded with copper oxide - Google Patents
Preparation method and application of cerium-zirconium composite oxide catalyst loaded with copper oxide Download PDFInfo
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Abstract
The invention discloses a preparation method and application of cerium-zirconium composite oxide catalyst loaded with copper oxide. The preparation method comprises the following steps of: dissolving Cu salt, Ce salt and Zr salt in deionized water, slowly and dropwise adding the deionized water into dilute ammonia water, heating by microwave, depositing, filtering, washing, drying by microwave and baking at high temperature to obtain the cerium-zirconium composite oxide catalyst loaded with copper oxide. Compared with the preparation method of traditional catalysts, the preparation method of the catalyst has the advantages that the preparation process is simple, the working hour is short, and CuO as an active component is highly dispersed on the surface of a carrier. The catalyst prepared by using the preparation method has very high anti-sintering capability and heat stability and has higher activity for CO catalytic oxidation reaction.
Description
Technical field
The present invention relates to a kind of high activity cerium zirconium compound oxide Preparation of catalysts method and application thereof of loaded copper oxide.
Background technology
CeO
2Be rare earth oxide significant in the Industrial Catalysis, its most important functions is the cushioning effect that plays oxygen in the concussion atmosphere of the continuous conversion of richness combustion/poor combustion, by oxidation state CeO
2With go back ortho states Ce
2O
3Between conversion, the oxygen of having strengthened material stores and releasability.It can be used for poison protection, tobacco of purifying vehicle exhaust processing, alcohols steam reforming hydrogen manufacturing, water gas shift reaction, CO and fall reactions such as removing of evil and closed system CO.
But at high temperature pure CeO
2Generation sintering, particle are grown up easily.Discover that the interpolation of Zr can stop CeO effectively
2Sintering, particularly the cerium zirconium sosoloid of Sheng Chenging has higher oxygen storage capacity and heat endurance.With the cerium zirconium sosoloid is carrier, the catalyst of the prepared one-tenth of noble metal such as load Au, Pt, Pd has excellent catalysis CO low-temperature oxidation activity, but, limited it in industrial extensive use owing to it costs an arm and a leg, natural resources is rare and reasons such as sulfur poisoning take place easily.Thereby impel people to turn to research to non-precious metal catalyst, especially with Ce
xZr
1-xO
2Become the focus of people's research for the research of the catalyst of carrier loaded base metal CuO.
CuO/Ce
xZr
1-xO
2The reactivity worth of catalyst is not only relevant with its composition, but also closely related with its preparation method.At present, preparation CuO/Ce
xZr
1-xO
2The method of catalyst can be divided into two kinds: one-step method and two-step method (infusion process).One-step method is the saline mixed solution employing precipitation method with copper, cerium, zirconium, obtains the sediment presoma of cupric, cerium, zirconium through precipitation, filtration, drying; Or adopt firing method or sol-gel process to obtain containing three's salt presoma three's the mixed solution.Above-mentioned gained presoma high-temperature roasting certain hour under air atmosphere just can be prepared copper cerium zirconium compound oxide catalyst.CuO is except that loading on the cerium zirconium sosoloid surface for this kind activity of such catalysts component, and quite a few has been inserted in the ceria lattice, can not contact with oxidized gas is fine, has therefore reduced its catalytic activity.Patent publication No. CN101069843A (2007) adopts one-step method to prepare CuO/Ce
0.8Zr
0.2O
2Catalyst has added cationic surfactant and precipitating reagent NaOH in preparation process, therefore, need wash by a large amount of deionized waters in the postorder processing links of catalyst, causes Preparation of catalysts long man-hour, and energy consumption is big.
Two-step method that is infusion process are at first prepared Ce by the precipitation method, sol-gel process etc.
xZr
1-xO
2Carrier is immersed in carrier surface with active ingredient copper then, promptly gets catalyst sample by heating concentrated solvent, oven dry, roasting.The weak point of this method is that carrier and Preparation of catalysts will be through twice drying and roastings, and preparation process is loaded down with trivial details, and man-hour is longer.Paper Applied Catalysis A:General 242 (2003) 151-159 adopt two-step method to prepare CuO/Ce
0.8Zr
0.2O
2Catalyst prepares Ce with sol-gel process earlier
0.8Zr
0.2O
2Carrier arrives Cu (NO with carrier impregnation then
3)
23H
2In the O solution, through 650 ℃ of obtained CuO of roasting 4h of 120 ℃ of dryings (10%)/Ce
0.8Zr
0.2O
2Three reduction peak appear in the TPR spectrogram of catalyst, and it is not too even to illustrate that active component CuO disperses at carrier surface, has bulky grain CuO to exist.Paper Journal of molecular CatalysisA:Chemical 255 (2006) 254-259 adopt Preparation by Uniform Precipitation Ce earlier
0.5Zr
0.5O
2Carrier joins carrier then and heats concentrated solvent in the copper nitrate solution, makes CuO/Ce through 500 ℃ of roastings of 100 ℃ of dryings
0.5Zr
0.5O
2Catalyst, three reduction peak also appear in the TPR collection of illustrative plates of this catalyst, illustrate also to have oarse-grained CuO, and oarse-grained CuO have inhibitory action to the CO low-temperature oxidation activity.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome prior art for preparing CuO/Ce
xZr
1-xO
2The catalyst process is loaded down with trivial details, elapsed time is long, or is used for the not high shortcoming of CO low-temperature oxidation activity.The method of the high activity cerium zirconium compound oxide catalyst that a kind of one-step method prepares loaded copper oxide is provided.
Technical scheme of the present invention
A kind of cerium zirconium compound oxide Preparation of catalysts method of loaded copper oxide comprises the following steps:
(1), Ce salt, Zr salt and Cu salt are dissolved in the deionized water, under 600～900r/min stirs, be added drop-wise in the ammonia spirit with the rate of addition of 0.8～1.2mL/min, drip finish after, continue again to stir 1h, must react suspension;
Above-mentioned Ce salt, Zr salt and Cu salt are their nitrate or carbonate; The ratio of the amount of substance of Ce salt and Zr salt (being molal quantity) is 0.5～0.9: 0.1～0.5, and wherein mantoquita adds
Go into amount and account for 2.04%～100% of Ce salt and the total amount of substance sum of Zr salt;
Ce salt, Zr salt and the Cu salt total concentration of metal ions in deionized water is 0.1～0.2mol/L.
The mass fraction of ammonia spirit is 5～8%, and wherein the amount of substance of ammonia is 12～18 times of amount sum of total metal ion species of Ce salt, Zr salt and Cu salt;
(2), the reaction suspension of step (1) gained is put into micro-wave oven,, carry out heating using microwave and be back to reactant liquor pH=6～7 o'clock, stop to add hot reflux with the mixing speed of 700～900r/min;
(3), reactant liquor that step (2) heated by microwave is refluxed filters when being chilled to 80～90 ℃, and with the absolute ethanol washing filter cake of 2～3 times of filter cake quality 2～3 times;
(4), the resulting filter cake of step (3) put into micro-wave oven control temperature be not more than 120 ℃, behind the heating, drying, again in Muffle furnace with 500～800 ℃ of roasting 2h, promptly get a kind of high activity cerium zirconium compound oxide catalyst of loaded copper oxide.
The cerium zirconium compound oxide catalyst of a kind of loaded copper oxide of above-mentioned preparation method's gained, form by two parts:
A part is the cerium zirconium compound oxide carrier, and another part CuO is an active component;
The cerium zirconium compound oxide carrier, its molecular formula is: Ce
xZr
1-xO
2, x=0.5～0.9 wherein, 1-x=0.5～0.1, promptly the ratio of cerium, zirconium atom number is 0.5～0.9: 0.1～0.5;
The CuO active constituent loading is on the cerium zirconium compound oxide carrier, and the CuO active component accounts in the catalyst 2%～50% of total amount of substance percentage composition (being molar content).
The cerium zirconium compound oxide catalyst of a kind of loaded copper oxide of preparation method's gained of the present invention is applicable to the CO catalytic oxidation.
Beneficial effect of the present invention
The present invention obtains cerium, zirconium precipitation of hydroxide suspension by coprecipitation, and under stirring fast, heating using microwave refluxes, [Cu (NH
3)
4] (OH)
2Decompose, the cupric oxide of generation or Kocide SD load on cerium, the zirconium hydroxide suspension particle surface, and after filtration, oven dry, roasting make catalyst of the present invention, its preparation process is simple, man-hour short, and active component CuO high degree of dispersion is at carrier surface.The catalyst of gained has very high anti-caking power and heat endurance, and the CO catalytic oxidation is had higher activity.
Below in conjunction with embodiment the present invention is further set forth, but do not limit the present invention.
Embodiment 1
With 5.211g Ce (NO
3)
36H
2O, 5.1506g Zr (NO
3)
45H
2O and 0.1183g Cu (NO
3)
23H
2O is dissolved in the 200mL deionized water, and with the rate of addition of 0.8～1.2mL/min it being added drop-wise to the 100mL mass fraction under the stirring of 600～900r/min is in 5%～8% the ammonia spirit.Drip and finish, continue to stir 1h again.Carry out heating using microwave with the mixing speed of 700～900r/min and reflux, o'clock stop heating until pH=6～7.When being chilled to 80～90 ℃, filters mixed liquor the absolute ethanol washing filter cake that usefulness filter cake quality is 2～3 times 2 times.After filter cake put into the micro-wave oven heating, drying, and in Muffle furnace 600 ℃ of roasting 2h, make catalyst A, the amount of substance percentage composition of CuO is 2% in this catalyst.
Embodiment 2
With 3.9083g Ce (NO
3)
36H
2O, 2.5753g Zr (NO
3)
45H
2O and 0.4027g Cu (NO
3)
23H
2O is dissolved in the 150mL deionized water, and with the rate of addition of 0.8～1.2mL/min it being added drop-wise to the 70mL mass fraction under the stirring of 600～900r/min is in 5%～8% the ammonia spirit.Drip and finish, continue to stir 1h again.Carry out heating using microwave with the mixing speed of 700-900r/min and reflux, o'clock stop heating until pH=6～7.When being chilled to 80～90 ℃, filters mixed liquor the absolute ethanol washing filter cake that usefulness filter cake quality is 2～3 times 2 times.After filter cake put into the micro-wave oven heating, drying, and in Muffle furnace 600 ℃ of roasting 2h, make catalyst B, the amount of substance percentage composition of CuO is 10% in this catalyst.
Embodiment 3
With 3.9083g Ce (NO
3)
36H
2O, 2.5753g Zr (NO
3)
45H
2O and 0.906g Cu (NO
3)
23H
2O is dissolved in the 160mL deionized water, and with the rate of addition of 0.8～1.2mL/min it being added drop-wise to the 100mL mass fraction under the stirring of 600～900r/min is in 5%～8% the ammonia spirit.Drip and finish, continue to stir 1h again.Carry out heating using microwave with the mixing speed of 700～900r/min and reflux, o'clock stop heating until pH=6～7.When being chilled to 80～90 ℃, filters mixed liquor the absolute ethanol washing filter cake that usefulness filter cake quality is 2～3 times 2 times.After filter cake put into the micro-wave oven heating, drying, and in Muffle furnace 600 ℃ of roasting 2h, make catalyst C, the amount of substance percentage composition of CuO is 20% in this catalyst.
Embodiment 4
With 4.3425g Ce (NO
3)
36H
2O, 1.8395g Zr (NO
3)
45H
2O and 1.841g Cu (NO
3)
23H
2O is dissolved in the 170mL deionized water, and with the rate of addition of 0.8～1.2mL/min it being added drop-wise to the 100mL mass fraction under the stirring of 600～900r/min is in 5%～8% the ammonia spirit.Drip and finish, continue to stir 1h again.Carry out heating using microwave with the mixing speed of 700～900r/min and reflux, o'clock stop heating until pH=6～7.When being chilled to 80～90 ℃, filters mixed liquor the absolute ethanol washing filter cake that usefulness filter cake quality is 2～3 times 2 times.After filter cake put into the micro-wave oven heating, drying, and in Muffle furnace 600 ℃ of roasting 2h, make catalyst D, the amount of substance percentage composition of CuO is 30% in this catalyst.
Embodiment 5
With 5.211g Ce (NO
3)
36H
2O, 1.2877g Zr (NO
3)
45H
2O and 2.4514g Cu (NO
3)
23H
2O is dissolved in the 200mL deionized water, and with the rate of addition of 0.8～1.2mL/min it being added drop-wise to the 100mL mass fraction under the stirring of 600～900r/min is in 5%～8% the ammonia spirit.Drip and finish, continue to stir 1h again.Carry out heating using microwave with the mixing speed of 700～900r/min and reflux, o'clock stop heating until pH=6～7.When being chilled to 80～90 ℃, filters mixed liquor the absolute ethanol washing filter cake that usefulness filter cake quality is 2～3 times 3 times.After filter cake put into the micro-wave oven heating, drying, and in Muffle furnace 600 ℃ of roasting 2h, make catalyst E, the amount of substance percentage composition of CuO is 40% in this catalyst.
Embodiment 6
With 6.948g Ce (NO
3)
36H
2O, 0.7632g Zr (NO
3)
45H
2O and 4.2952g Cu (NO
3)
23H
2O is dissolved in the 150mL deionized water, and with the rate of addition of 0.8～1.2mL/min it being added drop-wise to the 100mL mass fraction under the stirring of 600～900r/min is in 5%～8% the ammonia spirit.Drip and finish, continue to stir 1h again.Carry out heating using microwave with the mixing speed of 700～900r/min and reflux, o'clock stop heating until pH=6～7.When being chilled to 80～90 ℃, filters mixed liquor the absolute ethanol washing filter cake that usefulness filter cake quality is 2～3 times 3 times.After filter cake put into the micro-wave oven heating, drying, and in Muffle furnace 600 ℃ of roasting 2h, make catalyst F, the amount of substance percentage composition of CuO is 50% in this catalyst.
Embodiment 7
Preparation process is with embodiment 3,500 ℃ of roasting 2h in Muffle furnace, and the catalyst that makes is labeled as G.
Embodiment 8
Preparation process is with embodiment 3,700 ℃ of roasting 2h in Muffle furnace, and the catalyst that makes is labeled as H.
Embodiment 9
Preparation process is with embodiment 3,800 ℃ of roasting 2h in Muffle furnace, and the catalyst that makes is labeled as I.
Application Example 1
Catalyst prepared among the embodiment 1～9 is applied to the reaction of CO low-temperature oxidation.Being loaded in internal diameter after a certain amount of catalyst granules (40-60 order) quartz sand suitable with the triplication granule size mixed is 6mm, and length is in the stainless steel reaction pipe of 300mm.A certain amount of inert material of reaction tube bottom filling is as supporter.Adopt electrical heating, temperature is controlled automatically.By catalyst layer, carbon monoxide wherein is oxidized to carbon dioxide to unstripped gas from top to bottom.It is 1%CO, 10%O that unstripped gas is formed (volume fraction)
2, all the other are N
2, flow velocity is 40～60mLmin
-1Gas composition before and after the reaction is analyzed with the GC9790A type gas chromatograph that Wenling, Zhejiang Fu Li company produces, and hydrogen is carrier gas, thermal conductivity cell detector, carbon molecular sieve chromatographic column.The results are shown in Table 1 and table 2, as can be seen from Table 1, when reaction temperature is 85 ℃, the CuO load capacity is that the conversion ratio of 20% to 50% catalyst oxidation CO is higher, especially load capacity is 40% conversion fully, also relevant on the other hand with the content of cerium in the cerium zirconium compound oxide, along with the conversion ratio of the increase CO catalytic oxidation of cerium content is also increasing.As can be seen from Table 2, the CuO load capacity be 20% catalyst when sintering temperature is 600 ℃, the conversion ratio of CO catalytic oxidation is the highest.When sintering temperature was 800 ℃, this kind catalyst still had very high catalytic activity; When reaction temperature was 85 ℃, the conversion ratio of CO was 76.89%, illustrated that catalyst of the present invention has very high anti-caking power and heat endurance.
The CO oxidation activity of the different CuO load capacity of table 1 catalyst
Annotate: T
60, T
85Be respectively that the CO conversion ratio is the reaction temperature of 60% and 85% correspondence.
The CO oxidation activity of the different sintering temperature prepared catalyst of table 2
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (3)
1. the high activity cerium zirconium compound oxide Preparation of catalysts method of a loaded copper oxide is characterized in that:
Comprise the steps:
(1), Ce salt, Zr salt and Cu salt are dissolved in the deionized water, under 600～900r/min stirs, be added drop-wise in the ammonia spirit with the rate of addition of 0.8～1.2mL/min, drip finish after, continue again to stir 1h, must react suspension;
Above-mentioned Ce salt, Zr salt and Cu salt are their nitrate or carbonate; The ratio of the amount of substance of Ce salt and Zr salt is 0.5～0.9: 0.1～0.5, and wherein the addition of mantoquita accounts for 2.04%～100% of Ce salt and the total amount of substance sum of Zr salt;
Ce salt, Zr salt and the Cu salt total concentration of metal ions in deionized water is 0.1～0.2mol/L.
The mass fraction of ammonia spirit is 5～8%, and wherein the amount of substance of ammonia is 12～18 times of amount sum of total metal ion species of Ce salt, Zr salt and Cu salt;
(2), the reaction suspension of step (1) gained is put into micro-wave oven,, carry out heating using microwave and be back to reactant liquor pH=6～7 o'clock, stop to add hot reflux with the mixing speed of 700～900r/min;
(3), reactant liquor that step (2) heated by microwave is refluxed filters when being chilled to 80～90 ℃, and with the absolute ethanol washing filter cake of 2～3 times of filter cake quality 2～3 times;
(4), the resulting filter cake of step (3) put into micro-wave oven control temperature be not more than 120 ℃, behind the heating, drying, again in Muffle furnace with 500～800 ℃ of roasting 2h, promptly get a kind of high activity cerium zirconium compound oxide catalyst of loaded copper oxide.
2. the high activity cerium zirconium compound oxide Preparation of catalysts method of a kind of loaded copper oxide as claimed in claim 1 is characterized in that the catalyst of step (4) gained is made up of two parts:
A part is the cerium zirconium compound oxide carrier, and another part CuO is an active component;
The cerium zirconium compound oxide carrier, its molecular formula is: Ce
xZr
1-xO
2, x=0.5～0.9 wherein, 1-x=0.5～0.1, promptly the ratio of cerium, zirconium atom number is 0.5～0.9: 0.1～0.5;
The CuO active constituent loading is on the cerium zirconium compound oxide carrier, and the CuO active component accounts in the catalyst 2%～50% of total amount of substance percentage composition.
3. the high activity cerium zirconium compound oxide Preparation of catalysts method of a kind of loaded copper oxide as claimed in claim 1 is characterized in that the catalyst of step (4) gained is applied to the CO catalytic oxidation.
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