CN1814568A - NZP family coating-honeycomb cordierite ceramic composite carrier - Google Patents

NZP family coating-honeycomb cordierite ceramic composite carrier Download PDF

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CN1814568A
CN1814568A CN 200610010728 CN200610010728A CN1814568A CN 1814568 A CN1814568 A CN 1814568A CN 200610010728 CN200610010728 CN 200610010728 CN 200610010728 A CN200610010728 A CN 200610010728A CN 1814568 A CN1814568 A CN 1814568A
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coating
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nzp
cordierite ceramic
nzp family
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CN100364922C (en
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祝琳华
李良军
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention relates to a NZP family coating-beehive cordierite ceramic compounding carrier. It adopts carbonate of alkali metals or alkali earth metals, rOCl <SUB>2 </SUB>.8H<SUB> 2</SUB>O and (NH<SUB>4</SUB>) <SUB>2</SUB> HPO<SUB>4</SUB> as raw material, adding some organic additive, compounding slurry of NZP family coating by felting sol-gel method, coating the slurry on beehive cordierite ceramic, drying and sintering to gain NZP family coating-beehive cordierite ceramic compounding carrier. In the process of compound NZP family coating slurry, by controlling pH value and usage of kinds of raw material and organic additive, the pure NZP family compounding coating layer would be ensured. The thermal expansion coefficient is close to cordierite ceramic, thus, the thermal shock resistance would be enhanced, and it could be used as the carrier of three effects valuable metal catalyst used for purifying end gas.

Description

The NZP family coating-honeycomb cordierite ceramic composite carrier
Technical field:
The present invention relates to a kind of NZP family coating-honeycomb cordierite ceramic composite carrier, the metal catalyst technical field.
Background technology:
Vehicle-mounted three-way catalyst is generally used in the purification of vehicular emission tail gas, and this catalyzer is many by " γ-Al 2O 3Coating-honeycomb cordierite " composite carrier load noble metal active component constitutes, because CO, the NO in the cleaning of off-gas simultaneously XWith three kinds of pollutents of CH, so be called three-way catalyst.Because the exhaust temperature fluctuation range of motor vehicle emission is very big, and automobile is in the continuous motion, thus require three-way catalyst must can bear the intensive thermal shocking that vehicle exhaust temperature frequent variations causes catalyzer, not can so and breaking and Dusting.
For the three-way catalyst of loading type, its thermal shock resistance depends on its employed solid support material, and the three-effect catalysis agent carrier that present widely used purifying vehicle exhaust is used is with γ-Al 2O 3As second carrier, apply complex carrier " γ-Al that honeycomb-like cordierite forms 2O 3Coating-honeycomb cordierite ceramic ", trichroite belongs to low thermal expansion material, thus have good thermal shock resistance, but the specific surface area of honeycomb cordierite ceramic is less than 1m 2/ g can not satisfy the requirement of three-way catalyst contrast table area, therefore needs the γ-Al with bigger serface 2O 3Be coated in the surface of honeycomb cordierite ceramic with the form of coating, so the complex carrier that constitutes can guarantee the thermal shock resistance of catalyzer, can make the specific surface area of carrier meet the requirement of three-way catalyst to the bigger serface carrier again.
But, existing " γ-Al 2O 3Coating-honeycomb cordierite " there are following two problems in complex carrier:
1. because γ-Al 2O 3Belong to middle thermal expansion material, mean thermal expansion coefficients is 8.5 * 10 -6/ ℃, so (mean thermal expansion coefficients is 1.2 * 10 with the low thermal expansion material honeycomb cordierite -6/ ℃) matched coefficients of thermal expansion bad, influenced the interface bond strength between the two, when being subjected to frequent thermal shocking, γ-Al 2O 3Coating comes off easily, thereby has influenced the work-ing life of three-way catalyst.
2. γ-Al 2O 3Be a kind of metasable state, thermostability is bad, if temperature surpasses 800 ℃ crystal phase transition will take place in the use, causes the rapid reduction of specific surface area, thereby has influence on activity of such catalysts.
At the problems referred to above, the present invention replaces γ-Al with the NZP family material with ultra low heat expansion characteristic as coated material 2O 3Apply honeycomb cordierite ceramic and prepare a kind of NEW TYPE OF COMPOSITE carrier " NZP family coating-honeycomb cordierite ceramic ", because the matched coefficients of thermal expansion of NZP family coated material and cordierite ceramic is good, so can obtain resistance to sudden heating can better the NEW TYPE OF COMPOSITE carrier, the thermostability of NZP family material is better than γ-Al in addition 2O 3So, can obtain longer work-ing life with the three-way catalyst of this composite carrier load.
Up to now, do not find other open source literature identical report with the present invention.
Reference:
1.E.Breval，Agrawal?D?K.Thermal?expansion?characteristics?of[NZP]，NaZr 2P 3O 12-TypeMaterials：A?Review[J]Br?Ceram?Trans，1995，94(1)：27-32.
2. wish beautiful jade China, Liao Xuepin, Lang Xiaochuan, etc. phosphate ceramics Ca 1-xBa xZr 4(PO 4) 6Preparation and the heat shock resistance Journal of Sex Research [J] formed of zero thermal expansion thereof. Journal of Inorganic Materials, 2001,16 (3): 452-458.
3. peace qin, Feng Changgen, Ceng Qingxuan, etc. ceramic honeycomb carrier γ-Al 2O 3Coating progress [J]. chemistry circular, 2001,3:135-140.
4. Ceng Peilan, Huang Kelong, Liu Suqin, etc. Study on Automobile Exhaust Catalysts present situation and progress thereof [J]. material Leader, 2003,17 (3): 48-51.
5. Zhou Xueliang, Qin Yongning, horse intelligence. catalyzer [M]. Beijing: Chemical Industry Press, 2002,128-136.
Summary of the invention:
The objective of the invention is to further improve present technology, for the design and the production of three-way catalyst provides a kind of new NZP family coated material to be used to apply honeycomb cordierite ceramic, preparation " NZP family coating-honeycomb cordierite ceramic " complex carrier.The enforcement of this technology can obtain thermal shock resistance and thermostability can better complex carrier, is expected to obtain longer work-ing life with the triple effect noble metal catalyst of this composite carrier load.
Coated material of the present invention is the NZP family material with low thermal expansion characteristics, and this family's material has identical crystalline structure, and parent consists of NaZr 2P 3O 12, be called for short NZP, Na wherein +Can replace by other alkalimetal ion or by alkaline-earth metal ions and can not influence the performance of material, so NZP family material is a series of isostructural derivative MZr 2P 3O 12(M=Li +, Na +, K +, Rb +, Cs +) or MZr 4P 6O 24(M=Mg 2+, Ca 2+, Sr 2+, Ba 2+) and binary solid solution (as Sr 1-xK 2xZr 4P 6O 24, Ca 1-xSr xZr 4P 6O 24, Ca 1-xBa xZr 4P 6O 24Deng, 0＜x＜1 wherein) general designation.After the honeycomb cordierite ceramic process NZP family coated materials of low specific surface area, specific surface area can increase greatly, so be suitable as the carrier of three-way catalyst with the formed complex carrier of NZP family coated materials honeycomb cordierite ceramic " NZP family coating-honeycomb cordierite ceramic ".
The present invention adopts the dissolved colloidal state precursor of the synthetic NZP family of Complexing Sol-Gel Method coated material, the honeycomb cordierite ceramic that the Corning Incorporated of dip-coating at normal temperatures produces, through oven dry and high-temperature roasting, obtain the NZP family coating-honeycomb cordierite ceramic composite carrier then.
Complex carrier of the present invention is prepared by following method and step:
(1) really takes by weighing a certain amount of carbonate MCO 3(M=Mg 2+, Ca 2+, Sr 2+, Ba 2+) or M 2CO 3(M=Li +, Na +, K +), be dissolved in the ZrOCl that concentration is 0.5M 28H 2In the aqueous solution of O, obtain containing metallic cation M +Or M 2+And Zr 4+Solution;
(2) mol ratio according to metallic cation total in the reaction system and ethylenediamine tetraacetic acid (EDTA) and citric acid is respectively r 1=2 and r 2=1 ratio takes by weighing a certain amount of ethylenediamine tetraacetic acid (EDTA) and citric acid, earlier ethylenediamine tetraacetic acid (EDTA) is dissolved in the weak ammonia that volumetric molar concentration is 6M fully, obtain the ammonia soln of ethylenediamine tetraacetic acid (EDTA), then the ammonia soln of citric acid and ethylenediamine tetraacetic acid (EDTA) is joined successively (the NH of 1.0M 4) 2HPO 4In the aqueous solution, again according to the ratio r of ethylene glycol mole number with the total mole number of ethylenediamine tetraacetic acid (EDTA) and citric acid 3Ratio greater than 2 adds ethylene glycol, stirs to make above-mentioned 3 kinds of organic additives and (NH 4) 2HPO 4The solution uniform mixing; Carbonate, ZrOCl 28H 2O and (NH 4) 2HPO 4Consumption according to the accurate proportioning of stoichiometric relation of NZP family material;
What (3) front has been prepared contains metallic cation M +Or M 2+And Zr 4+Solution be added drop-wise to the (NH that has added 3 kinds of organic additives at normal temperature, under stirring 4) 2HPO 4React in the mixing solutions, when the above-mentioned solution that contains metallic cation is all joined (NH 4) 2HPO 4And after in the mixing solutions of additive, the pH value of regulating this reaction system with the weak ammonia of 6M is for greater than 7 alkaline range, the slurry that reaction is generated 70 ℃ down heating concentrate 3 hours, obtain the dissolved colloidal state presoma of NZP family material, be cooled to normal temperature then;
(4), 100 ℃ of following constant pressure and dries 24 hours,, promptly get " NZP family coating-honeycomb cordierite ceramic " complex carrier then again in 800 ℃ of following roastings 2 hours with above-mentioned colloidal sol dip-coating honeycomb cordierite ceramic at normal temperatures.Show that through the XRD analysis result this coating really is stable NZP group crystal compound.
(5) can repeatedly apply operation according to step (4) according to requirement to NZP family coating charge capacity.
" NZP family coating-honeycomb cordierite ceramic " of the present invention complex carrier has following advantage:
1.NZP the thermal expansivity of family's coating and honeycomb cordierite ceramic is very approaching, can guarantee that the two has better interface bond strength.
2.NZP the thermostability of family's coated material is better than at present the generally γ-Al of use 2O 3Coated material, the crystalline structure of NZP family material promptly can stable existence after 800 ℃ of formation, and the specific surface area variation of NZP group crystal compound is minimum in 800 ℃-1000 ℃ maturing temperature scope, for the thermostability that guarantees three-way catalyst is laid a good foundation.
3. through BET method test shows, after NZP family coated materials, the specific surface area of honeycomb cordierite ceramic can be increased to 10m 2/ g-20m 2/ g.
4. estimate through bench type triple effect reactive behavior with the noble metal catalyst of conventional immersion process for preparing with this new composite carrier load 1 (wt) %Pd, demonstrate good catalytic activity.
Embodiment:
Embodiment 1:
With chemical constitution is CaZr 4P 6O 24NZP family coated materials specification be honeycomb cordierite ceramic (its quality the be 110 gram) preparation " CaZr of φ 84 * 36mm 4P 6O 24Coating-cordierite honeycomb ceramic " complex carrier.According to making 50 gram CaZr 4P 6O 24Prepare burden the CaZr of actual needs 4P 6O 24The coating charge capacity is less than 30% of the honeycomb cordierite quality.
Accurately take by weighing 5.185 gram analytical pure CaCO 3Be dissolved in the ZrOCl that 410 ml concns are 0.5M 28H 2In the aqueous solution of O, obtain containing metallic cation Ca 2+, Zr 4+Solution;
Take by weighing 53.89 gram citric acids and 37.47 gram ethylenediamine tetraacetic acid (EDTA)s more respectively, ethylenediamine tetraacetic acid (EDTA) is dissolved in the weak ammonia that the 641mL volumetric molar concentration is 6M, obtain the ammonia soln of ethylenediamine tetraacetic acid (EDTA), then the ammonia soln of citric acid, ethylenediamine tetraacetic acid (EDTA) and 200 milliliters of ethylene glycol are joined the (NH of 308 milliliters of 1.0M 4) 2HPO 4In the aqueous solution, stir and make above-mentioned 3 kinds of organic additives and (NH 4) 2HPO 4The solution uniform mixing;
To contain metallic cation Ca 2+, Zr 4+Solution be added drop-wise to the (NH that contains 3 kinds of organic additives at normal temperature, under stirring 4) 2HPO 4React in the mixing solutions, when the above-mentioned solution that contains metallic cation is all joined (NH 4) 2HPO 4And after in the mixing solutions of additive, greater than 7 alkaline range, the slurry that reaction generates obtains the dissolved colloidal state presoma of NZP family material 70 ℃ of concentrated 3 hours of heating down, is cooled to normal temperature then with the pH value of the weak ammonia conditioned reaction system of 6M;
With above-mentioned colloidal sol dip-coating specification at normal temperatures is the honeycomb cordierite ceramic of φ 84 * 36mm, 100 ℃ of following constant pressure and dries 24 hours, in 800 ℃ of following roastings 2 hours, promptly gets " CaZr more then 4P 6O 24Coating-honeycomb cordierite ceramic " complex carrier.
Embodiment 2:
With chemical constitution is KZr 2P 3O 12NZP family coated materials specification be the honeycomb cordierite preparation " KZr of φ 84 * 36mm 2P 3O 12Coating-honeycomb cordierite ceramic " complex carrier.
Working method and step are with embodiment 1.Difference is: according to KZr 2P 3O 12Preparation amount be that 50 grams are prepared burden, the consumption of various raw materials and organic additive is different, specific as follows: need 6.89 gram analytical pure K 2CO 3, the ZrOCl of 395 milliliters of 0.5M 28H 2The aqueous solution of O, (the NH of 297 milliliters of 1.0M 4) 2HPO 4The aqueous solution, 62.24 gram citric acids, 43.28 gram ethylenediamine tetraacetic acid (EDTA)s (being dissolved in the weak ammonia that the 740mL volumetric molar concentration is 6M), 200 milliliters of ethylene glycol.
Embodiment 3:
With chemical constitution is Ca 0.85Ba 0.25Zr 4P 6O 24NZP family coated materials specification be the honeycomb cordierite preparation " Ca of φ 84 * 36mm 0.85Ba 0.25Zr 4P 6O 24Coating-honeycomb cordierite ceramic " complex carrier.
Working method and step are with embodiment 1.Difference is: according to Ca 0.85Ba 0.25Zr 4P 6O 24Preparation amount be that 50 grams are prepared burden, the consumption of various raw materials and organic additive is different, specific as follows: need 4.34 gram analytical pure CaCO 3With 1.49 gram analytical pure BaCO 3, the ZrOCl of 404 milliliters of 0.5M 28H 2The aqueous solution of O, (the NH of 303 milliliters of 1.0M 4) 2HPO 4The aqueous solution, 53.10 gram citric acids, 36.92 gram ethylenediamine tetraacetic acid (EDTA)s (being dissolved in the weak ammonia that the 632mL volumetric molar concentration is 6M), 200 milliliters of ethylene glycol; In addition, in the first step operation with CaCO 3And BaCO 3Be dissolved in the ZrOCl of 0.5M simultaneously 28H 2Get final product in the aqueous solution of O.

Claims (1)

1, a kind of NZP family coating-honeycomb cordierite ceramic composite carrier is characterized in that this complex carrier is prepared by following method and step:
(1) accurately takes by weighing a certain amount of carbonate MCO 3(M=Mg 2+, Ca 2+, Sr 2+, Ba 2+) or M 2CO 3(M=Li +, Na +, K +) be dissolved in the ZrOCl that concentration is 0.5M 28H 2In the aqueous solution of O, obtain containing metallic cation M +Or M 2+And Zr 4+Solution;
(2) mol ratio according to metallic cation total in the reaction system and ethylenediamine tetraacetic acid (EDTA) and citric acid is respectively r 1=2 and r 2=1 ratio, take by weighing ethylenediamine tetraacetic acid (EDTA) and citric acid respectively, earlier ethylenediamine tetraacetic acid (EDTA) is dissolved in the weak ammonia that volumetric molar concentration is 6M fully, obtains the ammonia soln of ethylenediamine tetraacetic acid (EDTA), then the ammonia soln of citric acid and ethylenediamine tetraacetic acid (EDTA) is joined successively (the NH of 1.0M 4) 2HPO 4In the aqueous solution, again according to the ratio r of ethylene glycol mole number with the total mole number of ethylenediamine tetraacetic acid (EDTA) and citric acid 3Ratio greater than 2 adds ethylene glycol, stirs to make above-mentioned 3 kinds of organic additives and (NH 4) 2HPO 4The solution uniform mixing; Carbonate, ZrOCl 28H 2O and (NH 4) 2HPO 4Consumption according to the preparation amount of the NZP family material of a certain concrete chemical constitution, according to the accurate proportioning of stoichiometric relation of this NZP family material;
What (3) front has been prepared contains metallic cation M +Or M 2+And Zr 4+Solution be added drop-wise to the (NH that has added 3 kinds of organic additives at normal temperature, under stirring 4) 2HPO 4React in the mixing solutions, when the above-mentioned solution that contains metallic cation is all joined (NH 4) 2HPO 4And after in the mixing solutions of additive, the pH value of regulating this reaction system with the weak ammonia of 6M is for greater than 7 alkaline range, the slurry that reaction is generated 70 ℃ down heating concentrate 3 hours, obtain the dissolved colloidal state presoma of NZP family material, be cooled to normal temperature then;
(4), 100 ℃ of following constant pressure and dries 24 hours, in 800 ℃ of following roastings 2 hours, promptly get the NZP family coating-honeycomb cordierite ceramic composite carrier more then with above-mentioned colloidal sol dip-coating honeycomb cordierite ceramic at normal temperatures; The operation of this step can be carried out repeatedly repeatedly, till the charge capacity of NZP family coating reaches requirement.
CNB2006100107288A 2006-03-06 2006-03-06 NZP family coating-honeycomb cordierite ceramic composite carrier Expired - Fee Related CN100364922C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093073A (en) * 2010-12-09 2011-06-15 杭州诺贝尔集团有限公司 Honeycomb ceramic and production method thereof
CN102616809A (en) * 2012-03-29 2012-08-01 昆明理工大学 Preparation method for NZP family mesoporous phosphate molecular sieve CaZr4P6O24
CN107225668A (en) * 2016-03-25 2017-10-03 日本碍子株式会社 The manufacture method of ceramic structure

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0717440B2 (en) * 1989-09-07 1995-03-01 日本碍子株式会社 Heat-resistant phosphate sintered body and method for producing the same
AU7616300A (en) * 1999-10-05 2001-05-10 Corning Incorporated Refractory nzp-type structures and method of making and using same
CN1569974A (en) * 2004-04-26 2005-01-26 昆明理工大学 Plural oxide nanocoating and its making method and uses

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093073A (en) * 2010-12-09 2011-06-15 杭州诺贝尔集团有限公司 Honeycomb ceramic and production method thereof
CN102616809A (en) * 2012-03-29 2012-08-01 昆明理工大学 Preparation method for NZP family mesoporous phosphate molecular sieve CaZr4P6O24
CN107225668A (en) * 2016-03-25 2017-10-03 日本碍子株式会社 The manufacture method of ceramic structure

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