CN107442119B - A kind of cerium oxide/zirconium oxide paper mold catalyst and preparation method thereof - Google Patents
A kind of cerium oxide/zirconium oxide paper mold catalyst and preparation method thereof Download PDFInfo
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- CN107442119B CN107442119B CN201710680350.0A CN201710680350A CN107442119B CN 107442119 B CN107442119 B CN 107442119B CN 201710680350 A CN201710680350 A CN 201710680350A CN 107442119 B CN107442119 B CN 107442119B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 42
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 42
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000835 fiber Substances 0.000 claims abstract description 108
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000000243 solution Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- 229940068984 polyvinyl alcohol Drugs 0.000 claims abstract description 15
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000005360 mashing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 23
- 229910052726 zirconium Inorganic materials 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052684 Cerium Inorganic materials 0.000 claims description 19
- 238000009987 spinning Methods 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011490 mineral wool Substances 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 9
- 239000000779 smoke Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 17
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052863 mullite Inorganic materials 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FPFFWBASMNDQQY-UHFFFAOYSA-N [Ca].[Na].[B] Chemical compound [Ca].[Na].[B] FPFFWBASMNDQQY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 borate compound Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/58—
-
- B01J35/60—
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
Abstract
The present invention relates to catalyst material preparation technical fields, specifically disclose a kind of cerium oxide/zirconium oxide paper mold catalyst and preparation method thereof, CeO2‑ZrO2Fiber and ceramic fibre, wherein the CeO2‑ZrO2The diameter of fiber is 5 ~ 10 μm, length 1-100cm；The catalyst with a thickness of 2 ~ 5mm, porosity 70% ~ 90%.The preparation method.The preparation method includes: the CeO that big L/D ratio is prepared using centrifugal drying silk method2‑ZrO2Fiber；Then cooperate ceramic fibre, inorganic binder, poly-vinyl alcohol solution mashing, pour into sheet forming apparatus, and remove water through vacuum suction filter, form, high temperature furnace roasts, and dipping, dry roasting obtain CeO in active component salt solution2‑ZrO2Paper mold catalyst.The corresponding temperature of carbon-smoke combustion maximum rate of catalyst prepared by the present invention is between 350-420 DEG C.
Description
Technical field
The present invention relates to catalyst material preparation technical field more particularly to a kind of cerium oxide/zirconium oxide paper mold catalyst
And preparation method thereof.
Background technique
Catalytic combustion technology is improving combustion process, is reducing reaction temperature, promotes completely burned and inhibit noxious material shape
There is highly significant effect at aspect, thus becomes the key technology of the application fields such as fuel cell, exhaust-gas treatment.Catalyst is
The core of catalytic combustion technology, it must have suitable shape, size and mechanical strength, to meet the operation of industrial reactor
It is required that.Paper mold catalyst is a kind of novel monolithic catalyst, since, porosity small with specific gravity are high and gas diffusion is good
Advantage is present material so as to effectively improving catalytic activity, reducing noble metal loadings and extending catalyst service life
One of with the research hotspot of catalytic field.
Currently, mainly having about the research of paper mold catalyst in the world: Kyushu University Takuya Kitaoka et al.
By using different noble metal active components (Pt, Cu, Ag, Au etc.) and different matrix fibers (fiber C, SiC fiber, pottery
Porcelain fiber, ZnO whisker, cellulose fibre etc.), and to matrix fiber carry out modified with functional group, have studied ethane dehydrogenation aoxidize,
The catalytic performance of toluene removal, CO catalysis oxidation, NOx catalysis reduction, self-heating reforming hydrogen manufacturing etc..Argentinian UNL-
The V.G.Milt at CONICET catalyticing research center et al. has bigger serface in matrix ceramic fibre and cellulose fibre load
With the Y-Shaped zeolite of porosity, for improving paper mold catalyst activity, simultaneous selection borate compound (especially sodium boron
Calcium stone) it is used to improve mechanical property as binder.So far, the domestic correlative study report that there is no paper mold catalyst and maturation
Market product.
Cerium oxide (CeO2) it is used as a kind of typical rare earth oxide, it is mainly characterized by distinctive superpower storage itself
Oxygen ability and valence electron constructure (Ce3+/Ce4+Between there is lower electrode electromotive force), be acknowledged as a kind of ideal catalyst and carry
Body.Later it was found that with simple CeO2It compares, adulterates Zr4+Plasma can more efficiently raising CeO2Storage
Oxygen ability carries out oxidation-reduction reaction at a lower temperature, while structure thermal stability and mechanical property can also be made to have
It is obviously improved, and significantly improves catalytic activity.Currently, people utilize a variety of hands such as electrical spinning method, hard template and dry spin processes
Section has developed a series of CeO2-ZrO2Fibrous material.But since intrinsic mechanical property is poor, cerium-based composite oxides fiber is selected to make
Constructing paper mold catalyst for matrix, there are larger difficulty.
Summary of the invention
For existing CeO2-ZrO2The intrinsic mechanical property of fibrous material is poor, and constructing paper mold catalyst, there are larger difficulty etc. to ask
Topic, the present invention provide a kind of cerium oxide/zirconium oxide paper mold catalyst.
Further, the present invention also provides a kind of cerium oxide/zirconium oxide paper mold catalyst preparation methods.
To achieve the above object of the invention, the embodiment of the present invention uses the following technical solution:
A kind of cerium oxide/zirconium oxide paper mold catalyst, CeO2-ZrO2Fiber and ceramic fibre, wherein the CeO2-ZrO2
The diameter of fiber is 5~10 μm, length 1-100cm；The catalyst with a thickness of 2~5mm, porosity 70%~90%.
The CeO of use2-ZrO2Fiber Aspect Ratio is big, there is certain mechanical strength, convenient for cutting, to realize and be chopped not
Carry out the matched well of mineral wool, therefore the paper mold catalyst uniformity and flexibility significantly improve.
A kind of preparation method of cerium oxide/zirconium oxide paper mold catalyst, the preparation method at least include the following steps:
Step 1, preparation CeO2-ZrO2Fiber: using zirconium oxycarbonate as zirconium source, zirconium oxycarbonate, carboxylic acid, water, cerium source are mixed
Conjunction obtains clear solution, and then the clear solution is concentrated under reduced pressure, and obtains the precursor sol that viscosity is 30~80Pas and spins
Silk liquid；Precursor sol spinning solution is subjected to centrifugal spinning, obtains precursor fibre；The precursor fibre is placed in sintering furnace
It is inside heat-treated, obtains CeO2-ZrO2Fiber；
Step 2, with slurry, mashing: CeO is weighed2-ZrO2Fiber, ceramic fibre, inorganic binder, poly-vinyl alcohol solution are added
Into reactor, slurries are stirred to get；
Step 3, molding: the slurries are poured into sheet forming apparatus, vacuum suction filter water removal, handsheet molding, 80~120
It is dry at a temperature of DEG C, obtain body paper；
Step 4, heat treatment: the body paper is heated into 1~2h under the conditions of 350~500 DEG C, obtains CeO2-ZrO2Compound fibre
Tie up paper；Step 5, by the CeO2-ZrO2Composite fibre paper, which is put into the active component salt solution that mass concentration is 20-40%, to be soaked
Stain, washing, drying, is then heat-treated, and CeO is obtained2-ZrO2Paper mold catalyst.
Compared with the existing technology, cerium oxide provided by the invention/zirconium oxide paper mold catalyst preparation method has following
The utility model has the advantages that
(1) CeO prepared by the present invention2-ZrO2Fiber Aspect Ratio is big, there is certain mechanical strength, convenient for cutting, thus real
The matched well with chopped mullite fiber is showed, therefore acquired copy paper slurries suspension and stability is good, CeO2-ZrO2
The uniformity and flexibility of fibrous paper significantly improve；
(2) inorganic binder that the present invention uses can be cerium colloidal sol, for improving CeO2-ZrO2Paper mold catalyst is urged
Changing activity has preferable booster action.In addition, due to the diffusion of gas and heat in paper mold catalyst will due to particle,
The traditional catalysts form such as spherical, honeycomb, plate, so that such catalyst is in volatile organic matter (VOC), carbon monoxide
(CO), the exhaust fume catalytics process field such as soot has a good application prospect, and practical application can fill up domestic market blank.
(3) CeO of this programme2-ZrO2The related technology of preparing mature and reliable of paper mold catalyst, mechanical property and catalysis are lived
Property is good, practical.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is CeO prepared by the embodiment of the present invention 12-ZrO2Fibre digital photo；
Fig. 2 is CeO prepared by the embodiment of the present invention 12-ZrO2The digital photograph of paper mold catalyst；
Fig. 3 is CeO prepared by the embodiment of the present invention 12-ZrO2The stereoscan photograph of paper mold catalyst；
Fig. 4 is CeO prepared in embodiment 1,5 of the present invention2-ZrO2The carbon soot particles combustion activity of paper mold catalyst
Schematic diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of cerium oxide/zirconium oxide paper mold catalyst, and the catalyst includes CeO2-ZrO2It is fine
Peacekeeping ceramic fibre, wherein the CeO2-ZrO2The diameter of fiber is 5~10 μm, length 1-100cm；The catalyst
With a thickness of 2~5mm, porosity 70%~90%.
Preferably, the ceramic fibre is mullite fiber, carbon fiber, alumina fibre, Zirconium oxide fibre, silicon carbide fibre
One of dimension.
Further, the present invention also provides a kind of cerium oxide/zirconium oxide paper mold catalyst preparation method, the preparation sides
Method at least includes the following steps:
Step 1, preparation CeO2-ZrO2Fiber: using zirconium oxycarbonate as zirconium source, zirconium oxycarbonate, carboxylic acid, water, cerium source are mixed
Conjunction obtains clear solution, and then the clear solution is concentrated under reduced pressure, and obtains the precursor sol that viscosity is 30~80Pas and spins
Silk liquid；Precursor sol spinning solution is subjected to centrifugal spinning, obtains precursor fibre；The precursor fibre is placed in sintering furnace
It is inside heat-treated, obtains CeO2-ZrO2Fiber；
Step 2, with slurry, mashing: CeO is weighed2-ZrO2Fiber, ceramic fibre, inorganic binder, poly-vinyl alcohol solution are added
Into reactor, slurries are stirred to get；
Step 3, molding: the slurries are poured into sheet forming apparatus, vacuum suction filter water removal, handsheet molding, 80~120
It is dry at a temperature of DEG C, obtain body paper；
Step 4, heat treatment: the body paper is heated into 1~2h under the conditions of 350~500 DEG C, obtains CeO2-ZrO2Compound fibre
Tie up paper；Step 5, by the CeO2-ZrO2Composite fibre paper, which is put into the active component salt solution that mass concentration is 20-40%, to be soaked
Stain, washing, drying, is then heat-treated, and CeO is obtained2-ZrO2Paper mold catalyst.
Explanation is further explained to above-mentioned preparation method below:
Preferably, zirconium oxycarbonate in the step 1, carboxylic acid, water molar ratio be 1:(2~3): (15~25), it is described
The molar ratio in zirconium oxycarbonate and the cerium source is 9:(1~9), and the cerium source is one of cerous nitrate or ammonium ceric nitrate,
The carboxylic acid is one of glacial acetic acid, formic acid, citric acid.
Preferably, in the step 2, CeO2-ZrO2The matter of fiber, ceramic fibre, inorganic binder, poly-vinyl alcohol solution
Amount than be 10:(1-5): (3-5): (100-500), the inorganic binder be mass concentration be 20-30% cerium colloidal sol, silicon it is molten
One of glue, Aluminum sol, zirconium colloidal sol.
Ceramic fibre has preferable stability, CeO2-ZrO2Both fiber has the performance of preferable storage oxygen, take
It is combined with each other, and modified by ceramic fibre, greatly enhances CeO2-ZrO2Store the performance of oxygen.
Preferably, the heating rate of sintering furnace described in the step 1 is 3~5 DEG C/min, and heat treatment condition is 300~450
DEG C, 1~2h.Preferably, heating rate is 0.5~10 DEG C/min in the step 4 or step 5, and heat treatment condition in step 5
It is 300~450 DEG C, 1~2h.
In heat treatment process, internal temperature will control uniformly as far as possible, heating rate and sintering temperature in sintering process
Design is suitable.Heating rate is excessively high, evaporates moisture too fast, will easily cause CeO2-ZrO2Fiber, CeO2-ZrO2It is multiple
Condensating fiber paper, CeO2-ZrO2The generation of paper mold deformation of catalyst particles and crackle, heating rate is too low to reduce production efficiency, heat preservation temperature
It is too short to spend low and time, can seriously affect intensity but be not that temperature is higher, the longer the better for soaking time, and temperature is high, the time
Long not only waste of energy increases cost.
Preferably, in the step 1 precursor sol spinning solution the preparation method comprises the following steps: first carboxylic acid, water are uniformly mixed, so
Afterwards at a temperature of 70-80 DEG C, zirconium oxycarbonate is added into the mixed solution of carboxylic acid and water, cerium is added under agitation
Source obtains the clear solution, then the clear solution is concentrated under reduced pressure to give to the presoma at a temperature of 70-80 DEG C molten
Glue spinning solution.
Preferably, centrifuge tube gets rid of a method process conditions in the step 1 are as follows: temperature: 30~70 DEG C, relative humidity: 20%
~50%, centrifuge speed: 2000~10000rpm gets rid of wire hole diameter: 0.02~0.2mm.
Preferably, it is 20-40% that active component salt solution, which is mass concentration, in the step 5, at least contains Cu2+、Mn2+、
Ni2+、Co3+One of, and the dip time is 15-120min.
By active component salt solution to CeO2-ZrO2Its catalytic activity can be improved in the dipping of composite fibre paper.
Embodiment provides in order to better illustrate the present invention, is illustrated below by embodiment is further.
Embodiment 1
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, preparation method includes the following steps:
Step 1, preparation CeO2-ZrO2Fiber: being respectively zirconium source and cerium source with zirconium oxycarbonate and cerous nitrate, according to alkali formula
Zirconium carbonate, glacial acetic acid, water molar ratio be 1:(2~3): (15~25), zirconium oxycarbonate, cerous nitrate molar ratio weigh for 3:1
Each component；First glacial acetic acid and water are uniformly mixed, at a temperature of 70-80 DEG C, zirconium oxycarbonate is added to glacial acetic acid and water
In mixed solution, fully reacting forms colourless transparent solution, while cerous nitrate quickly is added under conditions of stirring, then will be described
Clear solution is concentrated under reduced pressure at a temperature of 70-80 DEG C, obtains the precursor sol spinning solution that viscosity is 30~80Pas；Will before
It drives body colloidal sol spinning solution to move into centrifuge tube, method is got rid of using centrifuge tube and carries out centrifugal spinning, heat is kept using heater blower
Air flowing obtains precursor fibre；The precursor fibre is placed in sintering furnace and is warming up to the heating rate of 5 DEG C/min
500 DEG C, heat preservation 1h is heat-treated, and obtains CeO2-ZrO2Fiber, as shown in Figure 1.
Step 2, with slurry, mashing: 1000g CeO is weighed2-ZrO2Fiber, 100g mullite fiber, 300g mass concentration are
30% cerium colloidal sol, the poly-vinyl alcohol solution that 20Kg mass concentration is 1% are added in anti-stock tank, are uniformly mixing to obtain slurries；
Step 3, molding: the slurries are poured into sheet forming apparatus, vacuum suction filter water removal, handsheet molding, 80~120
It is dry at a temperature of DEG C, obtain body paper；
Step 4, heat treatment: rising to 500 DEG C from room temperature for the heating rate that the body paper is put into 5 DEG C/min in high temperature furnace,
Heat preservation 1h is heat-treated, and CeO is obtained2-ZrO2Composite fibre paper；
Step 5, by the CeO2-ZrO2Composite fibre paper is put into the Cu (NO that mass concentration is 30%3)2It is impregnated in solution
30min takes out washing, drying, is then placed in high temperature furnace and rises to 350 DEG C from room temperature with the heating rate of 10 DEG C/min, heat preservation
2h is heat-treated, and the CeO that porosity is up to 82% is obtained2-ZrO2Paper mold catalyst, as shown in Fig. 2.
Embodiment 2
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, respectively according to alkali formula in preparation methods steps 1
Zirconium carbonate, cerous nitrate molar ratio are 9:1,3:2,3:1,1:1, remaining process is as described in Example 1, repeats no more, and obtains respectively
Four kinds of cerium oxide/zirconium oxide paper mold catalyst.
Embodiment 3
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, step 2 in the preparation method: with slurry, beat
Slurry: 1000g CeO is weighed2-ZrO2Fiber, 250g mullite fiber, the cerium colloidal sol that 300g mass concentration is 30%, 20Kg mass
The poly-vinyl alcohol solution that concentration is 1% is added in anti-stock tank, is uniformly mixing to obtain slurries, remaining process is as described in Example 1,
It repeats no more.
Embodiment 4
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method steps 5: by the CeO2-
ZrO2Composite fibre paper is put into the Cu (NO that mass concentration is 30%3)230min is impregnated in solution, is taken out washing, drying, is then put
Enter in high temperature furnace and rise to 350 DEG C from room temperature with the heating rate of 5 DEG C/min, heat preservation 1h is heat-treated, obtain the cerium oxide/
Zirconium oxide paper mold catalyst；Remaining process is as described in Example 1, repeats no more.
Embodiment 5
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method steps 5: by the CeO2-
ZrO2Composite fibre paper, which is put into the active component solution that mass concentration is 30%, impregnates 30min, takes out washing, drying, then
It is put into high temperature furnace and rises to 350 DEG C from room temperature with the heating rate of 10 DEG C/min, heat preservation 2h is heat-treated, and the oxidation is obtained
Cerium/zirconium oxide paper mold catalyst；Remaining process is as described in Example 1, repeats no more.Wherein, the active component solution difference
Using Co (NO3)3、Mn(NO3)2、Ni(NO3)2, 3 kinds of cerium oxide/zirconium oxide paper mold catalyst is prepared respectively.
Embodiment 6
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, by the forerunner in the preparation method step 1
The heating rate that body fiber is placed in sintering furnace with 5 DEG C/min is warming up to 700 DEG C, and heat preservation 1h is heat-treated, and obtains CeO2-
ZrO2Fiber, remaining process is as described in Example 1, repeats no more.
The CeO for using sintering temperature to prepare for 700 DEG C2-ZrO2Fiber, average particle diameter size 20nm, fibre crystallinity compared with
CeO that is good, and obtaining2-ZrO2Composite fibre paper flexibility improves.
Embodiment 7
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, by the forerunner in the preparation method step 1
The heating rate that body fiber is placed in sintering furnace with 5 DEG C/min is warming up to 1000 DEG C, and heat preservation 1h is heat-treated, and obtains CeO2-
ZrO2Fiber, remaining process is as described in Example 1, repeats no more.
The CeO for using sintering temperature to prepare for 1000 DEG C2-ZrO2Fiber, average particle diameter size 55nm, fibre crystallinity
Preferably.
Embodiment 8
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method step 2: with slurry, mashing:
Weigh 1000g CeO2-ZrO2Fiber, 500g mullite fiber, the cerium colloidal sol that 300g mass concentration is 30%, 20Kg mass concentration
It is added in anti-stock tank for 1% poly-vinyl alcohol solution, is uniformly mixing to obtain slurries, remaining process is as described in Example 1, no longer
It repeats.
Embodiment 9
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method step 2: with slurry, mashing:
Weigh 1000g CeO2-ZrO2Fiber, 150g mullite fiber, the cerium colloidal sol that 500g mass concentration is 30%, 20Kg mass concentration
It is added in anti-stock tank for 1% poly-vinyl alcohol solution, is uniformly mixing to obtain slurries, remaining process is as described in Example 1, no longer
It repeats.
Embodiment 10
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method step 2: with slurry, mashing:
Weigh 1000g CeO2-ZrO2Fiber, 200g mullite fiber, the Aluminum sol that 300g mass concentration is 30%, 20Kg mass concentration
It is added in anti-stock tank for 1% poly-vinyl alcohol solution, is uniformly mixing to obtain slurries, remaining process is as described in Example 1, no longer
It repeats.
Embodiment 11
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method step 2: with slurry, mashing:
Weigh 1000g CeO2-ZrO2Fiber, 100g mullite fiber, the Aluminum sol that 300g mass concentration is 30%, 20Kg mass concentration
It is added in anti-stock tank for 1% poly-vinyl alcohol solution, is uniformly mixing to obtain slurries, remaining process is as described in Example 1, no longer
It repeats.
Embodiment 12
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method step 2: with slurry, mashing:
Weigh 1000g CeO2-ZrO2Fiber, 100g alumina fibre, the Aluminum sol that 300g mass concentration is 30%, 20Kg mass concentration
It is added in anti-stock tank for 1% poly-vinyl alcohol solution, is uniformly mixing to obtain slurries, remaining process is as described in Example 1, no longer
It repeats.
Embodiment 13
The present embodiment provides a kind of cerium oxide/zirconium oxide paper mold catalyst, the preparation method step 2: with slurry, mashing:
Weigh 1000g CeO2-ZrO2Fiber, 100g Zirconium oxide fibre, the Aluminum sol that 300g mass concentration is 30%, 20Kg mass concentration
It is added in anti-stock tank for 1% poly-vinyl alcohol solution, is uniformly mixing to obtain slurries, remaining process is as described in Example 1, no longer
It repeats.
Cerium oxide/zirconium oxide paper mold catalyst characteristic that embodiment provides in order to better illustrate the present invention below will
Embodiment 1, embodiment 3, embodiment 4, the paper mold catalyst of embodiment 8-13 preparation is respectively with soot by weight 10:1
It is uniformly mixed, CO under condition of different temperatures is measured under air conditions2Concentration, the corresponding temperature of carbon-smoke combustion maximum rate, knot
Fruit is as shown in table 1 below.
The corresponding temperature of 1 carbon-smoke combustion maximum rate of table
The paper mold catalyst for the different proportion that embodiment 2 is prepared respectively mixes with soot by weight 10:1 equal respectively
It is even, CO under condition of different temperatures is measured under air conditions2Concentration, the corresponding temperature of carbon-smoke combustion maximum rate are as a result as follows
Shown in table 2.
The corresponding temperature of 2 carbon-smoke combustion maximum rate of table
| n(ZrO2):n(CeO2) | Temperature |
| 9:1 | 420℃ |
| 3:2 | 380℃ |
| 3:1 | 366℃ |
| 1:1 | 350℃ |
By CeO prepared by embodiment 12-ZrO2Paper mold catalyst takes scanning electron microscope to be analyzed, as a result such as
Shown in Fig. 3.From figure 3, it can be seen that inorganic binder is uniformly attached to fiber surface, to guarantee that fibrous paper has preferable power
Learn property, while can see there are more holes between fiber and fiber, embody the loose porous spy of paper mold catalyst
Property, basis is provided for its practical application in fields such as catalysis, absorption.
By CeO prepared by embodiment 1, embodiment 52-ZrO2The carbon soot particles combustion activity schematic diagram of paper mold catalyst is such as
Shown in Fig. 4.As can be seen from Figure 4, active component takes Cu2+Paper mold catalyst the corresponding temperature of carbon-smoke combustion maximum rate it is minimum
It is 366 DEG C.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of cerium oxide/zirconium oxide paper mold catalyst, it is characterised in that: the catalyst includes CeO2-ZrO2Fiber and ceramics
Fiber, wherein the CeO2-ZrO2The diameter of fiber is 5~10 μm, length 1-100cm；The catalyst with a thickness of 2~
5mm, porosity 70%~90%；
The catalyst is prepared by following methods:
Step 1, preparation CeO2-ZrO2Fiber: using zirconium oxycarbonate as zirconium source, zirconium oxycarbonate, carboxylic acid, water, cerium source are mixed
To clear solution, then the clear solution is concentrated under reduced pressure, obtains the precursor sol spinning that viscosity is 30~80Pas
Liquid；Precursor sol spinning solution is subjected to centrifugal spinning, obtains precursor fibre；The precursor fibre is placed in sintering furnace
It is heat-treated, obtains CeO2-ZrO2Fiber；
Step 2, with slurry, mashing: CeO is weighed2-ZrO2Fiber, ceramic fibre, inorganic binder, poly-vinyl alcohol solution are added to instead
It answers in device, stirs to get slurries；
Step 3, molding: the slurries are poured into sheet forming apparatus, vacuum suction filter water removal, handsheet molding, in 80~120 DEG C of temperature
Lower drying is spent, body paper is obtained；
Step 4, heat treatment: the body paper is heated into 1~2h under the conditions of 350~500 DEG C, obtains CeO2-ZrO2Composite fibre
Paper；
Step 5, by the CeO2-ZrO2Composite fibre paper, which is put into active component salt solution, to be impregnated, and is washed, is dried, and is then carried out
Heat treatment obtains CeO2-ZrO2Paper mold catalyst.
2. cerium oxide as described in claim 1/zirconium oxide paper mold catalyst, it is characterised in that: the ceramic fibre is not come
At least one of mineral wool, carbon fiber, alumina fibre, Zirconium oxide fibre, silicon carbide fibre.
3. a kind of cerium oxide/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the preparation method include at least with
Lower step:
Step 1, preparation CeO2-ZrO2Fiber: using zirconium oxycarbonate as zirconium source, zirconium oxycarbonate, carboxylic acid, water, cerium source are mixed
To clear solution, then the clear solution is concentrated under reduced pressure, obtains the precursor sol spinning that viscosity is 30~80Pas
Liquid；Precursor sol spinning solution is subjected to centrifugal spinning, obtains precursor fibre；The precursor fibre is placed in sintering furnace
It is heat-treated, obtains CeO2-ZrO2Fiber；
Step 2, with slurry, mashing: CeO is weighed2-ZrO2Fiber, ceramic fibre, inorganic binder, poly-vinyl alcohol solution are added to instead
It answers in device, stirs to get slurries；
Step 3, molding: the slurries are poured into sheet forming apparatus, vacuum suction filter water removal, handsheet molding, in 80~120 DEG C of temperature
Lower drying is spent, body paper is obtained；
Step 4, heat treatment: the body paper is heated into 1~2h under the conditions of 350~500 DEG C, obtains CeO2-ZrO2Composite fibre
Paper；
Step 5, by the CeO2-ZrO2Composite fibre paper, which is put into active component salt solution, to be impregnated, and is washed, is dried, and is then carried out
Heat treatment obtains CeO2-ZrO2Paper mold catalyst.
4. cerium oxide as claimed in claim 3/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the step 1
Middle zirconium oxycarbonate, carboxylic acid, water molar ratio be 1:(2~3): (15~25), the zirconium oxycarbonate rub with the cerium source
You are than being 9:(1~9), and the cerium source is one of cerous nitrate or ammonium ceric nitrate, the carboxylic acid is glacial acetic acid, formic acid, lemon
One of lemon acid.
5. cerium oxide as claimed in claim 3/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the step 2
In, CeO2-ZrO2Fiber, ceramic fibre, inorganic binder, poly-vinyl alcohol solution mass ratio be 10:(1-5): (3-5):
(100-500), the inorganic binder is in the cerium colloidal sol that mass concentration is 20-30%, silica solution, Aluminum sol, zirconium colloidal sol
It is a kind of.
6. cerium oxide as claimed in claim 3/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the step 1
The heating rate of the sintering furnace is 3~5 DEG C/min, and heat treatment condition is 300~450 DEG C, 1~2h.
7. cerium oxide as claimed in claim 3/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the step 4
Or heating rate is 0.5~10 DEG C/min in step 5, and heat treatment condition is 300~450 DEG C in step 5,1~2h.
8. cerium oxide as claimed in claim 3/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the step 1
Middle precursor sol spinning solution the preparation method comprises the following steps: first carboxylic acid, water are uniformly mixed, then at a temperature of 70-80 DEG C, by alkali formula
Zirconium carbonate is added into the mixed solution of carboxylic acid and water, and cerium source is added under agitation, obtains the clear solution, then will
The clear solution is concentrated under reduced pressure to give the precursor sol spinning solution at a temperature of 70-80 DEG C.
9. cerium oxide as claimed in claim 3/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the step 1
Middle centrifugal spinning process condition are as follows: temperature: 30~70 DEG C, relative humidity: 20%~50%, centrifuge speed: 2000~
10000rpm gets rid of wire hole diameter: 0.02~0.2mm.
10. cerium oxide as claimed in claim 3/zirconium oxide paper mold catalyst preparation method, it is characterised in that: the step
It is 20-40% that active component salt solution, which is mass concentration, in 5, at least contains Cu2+、Mn2+、Ni2+、Co3+One of, and it is described
Dip time is 15-120min.
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