CN105148914A - Fe2O3/Al2O3/cordierite catalyst and preparation method thereof - Google Patents

Fe2O3/Al2O3/cordierite catalyst and preparation method thereof Download PDF

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CN105148914A
CN105148914A CN201510430256.0A CN201510430256A CN105148914A CN 105148914 A CN105148914 A CN 105148914A CN 201510430256 A CN201510430256 A CN 201510430256A CN 105148914 A CN105148914 A CN 105148914A
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cordierite
catalyst
preparation
roasting
drying
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苏亚欣
周皞
廖文裕
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Donghua University
National Dong Hwa University
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Donghua University
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Abstract

The invention relates to a Fe2O3/Al2O3/cordierite catalyst and a preparation method thereof. According to the invention, the catalyst comprises cordierite used as a carrier, an Al2O3 sol layer coated on the surface of the cordierite, and an iron oxide layer dispersed on the surface of the Al2O3 sol layer; the preparation method comprises the following steps: pretreatment of the carrier, preparation of aluminum sol, coating of the aluminum sol and impregnation of Fe(NO3)3; and NOX in industrial flue gas is removed with the Fe2O3/Al2O3/cordierite monolithic catalyst as the catalyst and with hydrocarbon as a reducing agent. The invention has the following beneficial effects: the aluminum sol is well coated on the surface of the cordierite, so a thin layer of amorphous aluminium oxide is formed; nanometer-grade iron oxide is uniformly dispersed on the aluminium oxide coating, so an SCR active center is formed; and the hydrocarbon is used as the reducing agent, so highly-efficient denitration efficiency is obtained.

Description

A kind of Fe 2o 3/ Al 2o 3/ cordierite catalyst and preparation method thereof
Technical field
The invention belongs to catalyst material and Synthesis and applications field thereof, particularly a kind of Fe 2o 3/ Al 2o 3/ cordierite catalyst and preparation method thereof.
Background technology
Current industrial smoke denitration SCR technique mainly uses NH 3eliminate NO as reducing agent, conventional catalyst is V 2o 5-WO 3/ TiO 2.Its subject matter existed is reducing agent NH 3cost higher and itself have certain toxicity, NH in technical process 3leakage and unreacted NH 3discharge can to environment; Catalytic component based on vanadium cost is higher, itself has toxicity, the easy secondary pollution problems of post processing.Due to hydrocarbon compound abundance, and at NO xthere is hydro carbons in pollution sources, take hydro carbons as reducing agent simultaneously, eliminates while the pollutant that can realize coexisting.The catalyst of transition metal oxide such as Fe, Cu, V, Ce are cheap, are usually used in catalytic oxidation-reduction reaction, but in existing domestic and foreign literature report, transition metal oxide class catalyst hydro carbons reductive NO x(HC-SCR) activity is lower.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Fe 2o 3/ Al 2o 3/ cordierite catalyst and preparation method thereof, Alumina gel is coated in well on cordierite surface, forms the amorphous alumina that one deck is very thin, nanometer ferro oxide is dispersed on aluminum oxide coating layer, form SCR activity center, be reducing agent with hydro carbons, there is efficient denitration efficiency.
A kind of Fe of the present invention 2o 3/ Al 2o 3/ cordierite catalyst, comprising: with carrier cordierite, Al 2o 3sol layer is coated on cordierite surface and iron oxide layer is scattered in Al 2o 3sol layer surface; By weight percentage, comprising: cordierite content is 70 ~ 80wt%, Al 2o 3content is 15 ~ 18wt%, Fe 2o 3content is 2 ~ 15wt%.
One of the present invention Fe as claimed in claim 1 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, comprising:
(1) cordierite is carried out pretreatment, obtain pretreated cordierite;
(2) above-mentioned pretreated cordierite is immersed A1 2o 3in colloidal sol, after 30 ~ 60min, take out, blow down unnecessary colloidal sol, then dry, roasting, repeats to A1 2o 3load capacity is 20 ~ 22wt%, obtains modification cordierite carrier;
(3) above-mentioned modification cordierite carrier be impregnated in 10 ~ 12h in the precursor solution of Fe, take out, blow down surplus liquid, dry, roasting, repeat aforesaid operations to Fe 2o 3load capacity is 2 ~ 15wt%, obtains Fe 2o 3/ Al 2o 3/ cordierite catalyst.
The middle cordierite of described step (1) carries out pretreatment and is specially: cordierite being put into concentration expressed in percentage by volume is 15% salpeter solution, room temperature treatment 12 ~ 24h, washing, 110 DEG C of drying 8 ~ 12h.
A1 in described step (2) 2o 3the preparation method of colloidal sol is: pour in container by Alumina gel precursor solution, heat under reflux in water-bath, and temperature rises to 75 ~ 80 DEG C, and adjust ph is 8 ~ 9,90 DEG C of backflows, and adjust ph is 3 ~ 4, leaves standstill, after solution clear, obtains A1 2o 3colloidal sol.
Described Alumina gel precursor solution is Al (NO 3) 3solution, concentration is 1.3 ~ 1.5mol/L.
Adding ammoniacal liquor adjust ph is 8-9; Concentration expressed in percentage by volume is 15% nitric acid titration adjust ph is 3 ~ 4.
In described step (2), drying is: 110 DEG C of drying 10 ~ 12h; Roasting is: 500 DEG C ~ 550 DEG C roasting 3 ~ 5h.
In described step (3), drying is: 100 ~ 120 DEG C of drying 10 ~ 12h; Roasting is: 500 DEG C ~ 550 DEG C roasting 5 ~ 6h.
In described step (3), the precursor solution of Fe is Fe (NO 3) 3solution, concentration is 0.8 ~ 1mol/L.
A kind of Fe/Al of the present invention 2o 3the application of/cordierite catalyst, Fe/Al 2o 3/ cordierite is catalyst, take hydro carbons as reducing agent, removes the NO in industrial smoke x.
In the present invention, Alumina gel is coated in well on cordierite surface, and form the amorphous alumina that one deck is very thin, nanometer ferro oxide is dispersed on aluminum oxide coating layer, forms SCR activity center, is reducing agent, has efficient denitration efficiency with hydro carbons.
beneficial effect
Iron dust is in transition elements, and chemical property is active, rich reserves on earth, and cost is lower, and compared with vanadium-tungsten-titanium catalyst series, ferrum-based catalyst has that environmental friendliness, catalytic activity are excellent, denitration low cost and other advantages; Cordierite honeycomb ceramic (2Al 2o 32MgO5SiO 2) there is lower thermal coefficient of expansion and outstanding thermal-shock resistance, widely use as catalyst substrate; Alumina gel is coated in well on cordierite surface, and form the amorphous alumina that one deck is very thin, nanometer ferro oxide is dispersed on aluminum oxide coating layer, forms SCR activity center, take hydro carbons as reducing agent, have efficient denitration efficiency.
Accompanying drawing explanation
Fig. 1 is different Fe 2o 3the Fe of load capacity 2o 3/ Al 2o 3the scanning electron microscopic picture of the amplification 10000 times of/cordierite monolithic catalyst finished product, wherein a:2%Fe 2o 3/ Al 2o 3/ CM (2wt%Fe 2o 3load capacity); B:6%Fe 2o 3/ Al 2o 3/ CM (6wt%Fe 2o 3load capacity); C:10%Fe 2o 3/ Al 2o 3/ CM (10wt%Fe 2o 3load capacity); D:15%Fe 2o 3al 2o 3/ CM (15wt%Fe 2o 3load capacity);
Fig. 2 is Fe 2o 3/ Al 2o 3the XRD collection of illustrative plates of/cordierite;
Fig. 3 is Fe 2o 3/ Al 2o 3xPS collection of illustrative plates (a) Fe2P of/cordierite, (b) Al2P;
Fig. 4 is Fe 2o 3/ Al 2o 3the H of/cordierite 2-TPR collection of illustrative plates.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) Vehicle element: honeycomb-like cordierite is put into 15% salpeter solution, room temperature treatment 24h, be then washed with distilled water to pH=7,110 DEG C of dry more than 12h.
(2) Alumina gel preparation: the Al (NO of preparation 1.3 ~ 1.5mol/L 3) 3solution is poured in three-neck flask, heats under reflux in water-bath, and temperature rises to 75 ~ 80 DEG C, and adding ammoniacal liquor adjust ph is reflux at 8 ~ 9,90 DEG C, and be then 3 ~ 4 with 15% nitric acid titration adjust ph, solution clear after a period of time, obtains A1 2o 3colloidal sol.
(3) coating of Alumina gel: the cordierite of step (1) nitric acid treatment is immersed the A1 that step (2) prepares 2o 3in colloidal sol, 30 ~ 60min, taking-up ear washing bulb blows down the colloidal sol in its passage, at 110 DEG C in drying box dry 10 ~ 12 hours, 500 DEG C of roasting 3 ~ 5h in Muffle furnace, repeats aforesaid operations three to four times to A1 2o 3load capacity increases to 20wt%.
(4) Fe (NO 3) 3dipping: preparation, the cordierite carrier of modification step (3) obtained impregnated in the Fe (NO of 0.8 ~ 1mol/L 3) 310 ~ 12h in solution, takes out and blows down remaining liq, at 100 ~ 120 DEG C in drying box dry 10 ~ 12 hours, and 500 DEG C of roasting 5 ~ 6h in Muffle furnace, repeat above being operated to and obtain predetermined Fe 2o 3load capacity 10wt%, obtains integral catalyzer finished product.
Fig. 1 is the scanning electron microscopic picture (amplifying 10000 times) of catalyst sample.Load 2wt%Fe 2o 3after, can be observed very small amount of nano particle and be distributed on alumina flake.Work as Fe 2o 3load capacity is more than after 10wt.%, and find that there is nanometer rods and generate, be distributed in catalyst surface brokenly, length is about 500nm.Along with Fe 2o 3load capacity be increased to 10wt.% further, start to reunite in catalyst surface nanometer rods.EDS detects and shows that nanometer rods main composition element is Fe.
Fig. 2 is the XRD testing result of catalyst sample.Load 2wt.%Fe 2o 3after, do not observe Fe 2o 3or the iron compound patterned features diffraction maximum of other form generates, iron species possibility high degree of dispersion is described or exists with amorphous state.As the Fe of catalyst 2o 3load capacity, more than 6wt.%, starts there is Fe 2o 3characteristic diffraction peak occurs, along with the further increase of Fe load capacity, and Fe 2o 3characteristic peak is grow gradually, shows Fe 2o 3degree of crystallinity improves.Judged by XRD and SEM, the Fe of length to be the nanometer rods of about 500nm be well-crystallized 2o 3.
Fig. 3 is Fe 2o 3/ Al 2o 3xPS collection of illustrative plates (a) Fe2P of/cordierite, (b) Al2P.Along with Fe load capacity is increased to 8wt.% from 2wt.%, Fe2p3/2 peak combine can spectral strength then grow gradually, in catalyst, iron species mainly exist with+3 valencys.It can size be 74.4eV that catalyst sample Al2p spectrogram display Al2p peak combines, and illustrates that most of aluminium oxide enters in the duct of the cordierite after acidifying.
Fig. 4 is Fe 2o 3/ Al 2o 3the H of/cordierite 2-TPR collection of illustrative plates.With analytically pure Fe 2o 3compare, Fe 2o 3/ Al 2o 3the reduction of/CM plays peak temperature and decreases, simultaneously Fe 2o 3/ Al 2o 3the high temperature peak corresponding temperature of/CM sample moves to low temperature direction, shows the Fe be distributed on carrier 2o 3nanometer rods has than pure Fe 2o 3stronger middle high temperature reduction ability.

Claims (10)

1. a Fe 2o 3/ Al 2o 3/ cordierite catalyst, is characterized in that: described catalyst take cordierite as carrier, Al 2o 3sol layer is coated on cordierite surface and nanometer Fe 2o 3rod is scattered in Al 2o 3sol layer surface; By weight percentage, comprising: cordierite content is 70 ~ 80wt%, Al 2o 3content is 15 ~ 18wt%, Fe 2o 3content is 2 ~ 15wt%.
2. a Fe as claimed in claim 1 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, comprising:
(1) cordierite is carried out pretreatment, obtain pretreated cordierite;
(2) above-mentioned pretreated cordierite is immersed A1 2o 3in colloidal sol, after 30 ~ 60min, take out, blow down unnecessary colloidal sol, then dry, roasting, repeats to A1 2o 3load capacity is 20 ~ 22wt%, obtains modification cordierite carrier;
(3) above-mentioned modification cordierite carrier be impregnated in 10 ~ 12h in the precursor solution of Fe, take out, blow down surplus liquid, dry, roasting, repeat aforesaid operations to Fe 2o 3load capacity is 2 ~ 15wt%, obtains Fe 2o 3/ Al 2o 3/ cordierite catalyst.
3. a kind of Fe according to claim 2 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, it is characterized in that: the middle cordierite of described step (1) carries out pretreatment and is specially: cordierite being put into concentration expressed in percentage by volume is 15% salpeter solution, room temperature treatment 12 ~ 24h, washs to PH=7,110 DEG C of drying 8 ~ 12h.
4. a kind of Fe according to claim 2 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, is characterized in that: A1 in described step (2) 2o 3the preparation method of colloidal sol is: pour in container by Alumina gel precursor solution, heat under reflux in water-bath, and temperature rises to 75 ~ 80 DEG C, and adjust ph is 8 ~ 9,90 DEG C of backflows, and adjust ph is 3 ~ 4, leaves standstill, after solution clear, obtains A1 2o 3colloidal sol.
5. a kind of Fe according to claim 4 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, is characterized in that: described Alumina gel precursor solution is Al (NO 3) 3solution, concentration is 1.3 ~ 1.5mol/L.
6. a kind of Fe according to claim 4 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, is characterized in that: adding ammoniacal liquor adjust ph is 8-9; Concentration expressed in percentage by volume is 15% nitric acid titration adjust ph is 3 ~ 4.
7. a kind of Fe according to claim 2 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, is characterized in that: in described step (2), drying is: 110 DEG C of drying 10 ~ 12h; Roasting is: 500 DEG C ~ 550 DEG C roasting 3 ~ 5h.
8. a kind of Fe according to claim 2 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, is characterized in that: in described step (3), drying is: 100 ~ 120 DEG C of drying 10 ~ 12h, roasting is: 500 DEG C ~ 550 DEG C roasting 5 ~ 6h.
9. a kind of Fe according to claim 2 2o 3/ Al 2o 3the preparation method of/cordierite catalyst, is characterized in that: in described step (3), the precursor solution of Fe is Fe (NO 3) 3solution, concentration is 0.8-1mol/L.
10. a Fe as claimed in claim 1 2o 3/ Al 2o 3the application of/cordierite catalyst, is characterized in that: Fe 2o 3/ Al 2o 3/ cordierite is catalyst, take hydro carbons as reducing agent, removes the NO in industrial smoke x.
CN201510430256.0A 2015-07-21 2015-07-21 Fe2O3/Al2O3/cordierite catalyst and preparation method thereof Pending CN105148914A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108554410A (en) * 2018-05-03 2018-09-21 东华大学 A kind of Fe/Ti-PILC catalyst, preparation method and application
CN109731609A (en) * 2019-01-07 2019-05-10 上海国瓷新材料技术有限公司 A kind of Cu-SSZ-13/ porous ceramic catalyst and the preparation method and application thereof that coating is controllable

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108554410A (en) * 2018-05-03 2018-09-21 东华大学 A kind of Fe/Ti-PILC catalyst, preparation method and application
CN109731609A (en) * 2019-01-07 2019-05-10 上海国瓷新材料技术有限公司 A kind of Cu-SSZ-13/ porous ceramic catalyst and the preparation method and application thereof that coating is controllable
CN109731609B (en) * 2019-01-07 2020-10-30 上海国瓷新材料技术有限公司 Cu-SSZ-13/porous ceramic catalyst with controllable coating and preparation method and application thereof

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