CN105126887A - Catalyst support body and preparation method and application thereof - Google Patents

Catalyst support body and preparation method and application thereof Download PDF

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CN105126887A
CN105126887A CN201510514920.XA CN201510514920A CN105126887A CN 105126887 A CN105126887 A CN 105126887A CN 201510514920 A CN201510514920 A CN 201510514920A CN 105126887 A CN105126887 A CN 105126887A
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catalyst support
carrier layer
matrix
sintering
powder
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CN105126887B (en
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高麟
汪涛
李波
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Intermet Technology Chengdu Co Ltd
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Abstract

The invention discloses a catalyst support body and a preparation method and an application thereof in an automobile tail gas catalyst; the catalyst support body includes a substrate and a carrier layer attaching to the substrate, wherein the substrate is mainly composed of a Ti3SiC2 porous material and/or a Ti3AlC2 porous material; the carrier layer is composed of an oxide in-situ generated on the substrate through oxidation of the substrate; the preparation process of the catalyst support body includes preparation of the substrate mainly composed of the Ti3SiC2 porous material and/or the Ti3AlC2 porous material and the carrier layer composed of the oxide prepared through oxidation of the substrate and in-situ generated on the substrate; the binding force between the carrier layer obtained through the in-situ oxidation method and in-situ generated on the substrate surface and the substrate is strong, so that the catalyst support body can bear vibration of cars, and the carrier layer is not easy to fall off; and the catalyst support body prepared by the method further has the advantages of large specific surface area, high porosity, small heat capacity, high thermal conductivity and the like.

Description

Catalyst support and its preparation method and application
Technical field
The present invention relates to a kind of new catalyst supporter, also relate to the preparation method of described catalyst support and its application in auto-exhaust catalyst.
Background technology
The performance of auto-exhaust catalyst supporter on the catalytic effect impact of catalyst greatly.Desirable catalyst support should possess following features: 1) enough mechanical strengths, vibrates to bear the adjustment thermal shock of air-flow and pavement roughness and cylinder the high vibration caused; 2) enough heat resistances, to adapt to the wider exhaust temperature ranges of automobile engine; 3) suitable pore structure or percent opening; 4) low thermal capacitance and high thermal conductivity, make it reach the temperature required time shorten of catalytic reaction, improves catalytic purification efficiency; 5) larger specific area, makes active component (mostly being noble metal) be evenly distributed, and is conducive to the utilization rate improving active component, reduces costs; 6) not containing the material making catalyst poisoning, and do not occur to interact with catalyst and affect the catalytic action of catalyst; 7) suitable water absorption rate, cheap price.
Due to cordierite (2MgOAl 2o 35SiO 2) advantage such as ceramic material has that thermal expansion system is lower, thermal-shock resistance is outstanding, current auto-exhaust catalyst supporter great majority are made up of cordierite.But the specific area of cordierite is less, generally only has 1m 2about/g, must apply the coating of one deck high-specific surface area, such as TiO 2, Al 2o 3, this coating is the carrier for supporting catalytic active material, and at this moment cordierite is then as matrix.In the catalyst support that conventional method prepares, the active force between cordierite substrates and carrier layer is more weak, causes the shock resistance of catalyst poor, is difficult to withstand the vibrations of automobile and carrier layer is come off, thus making catalyst loss of activity.
Summary of the invention
First problem to be solved by this invention is to provide a kind of novel catalyst support, has stronger adhesion between the matrix of this catalyst and carrier layer.In addition, the present invention also will provide the preparation method and application of this catalyst support.
Catalyst support of the present invention comprises matrix and is attached to the carrier layer on matrix, and described matrix is primarily of Ti 3siC 2porous material and/or Ti 3alC 2porous material is formed; Described carrier layer is by be oxidized matrix thus in-situ preparation is formed in the oxide of carrier surface; Described oxide comprises TiO 2or comprise Al 2o 3and SiO 2in at least one and TiO 2mixture.
The effect of the carrier layer in above-mentioned catalyst support provided by the invention is supporting catalytic active material.In the carrier layer of supporter of the present invention, the average grain diameter of oxide is 100-200nm, and the thickness of carrier is generally 50-200 μm, preferably 150-200 μm; The quality of carrier layer generally accounts for the 0.2-0.5% of supporter quality, preferably 0.35-0.5%.
On the catalytic effect impact of catalyst greatly, such as, catalyst needs while maintenance is compared with macroporsity and specific surface for the correlated performance of catalyst support, still has larger mechanical property and suitable thermal capacitance and thermal conductivity; Catalyst support provided by the invention can well be full of above-mentioned requirements, namely reaches following performance: porosity>=35% of this supporter, specific area>=25m 2/ g, tensile strength>=25MPa, thermal conductivity>=26W/m DEG C, thermal capacitance≤600J/kgK.
As can be seen from the above data, catalyst support provided by the invention is compared with existing supporter, and correlated performance has equal level, and these performances are primarily of Ti in matrix 3siC 2porous material and/or Ti 3alC 2porous material determined, but due to the special role of in-situ oxidation process, make the adhesion of matrix and carrier layer in supporter strong, carrier layer difficult drop-off, therefore catalyst support of the present invention has better shock resistance.
The important purposes of of above-mentioned catalyst support is the application in auto-exhaust catalyst.When this catalyst support is as auto-exhaust catalyst supporter, need the corresponding catalytic active substance of load in the carrier layer of this supporter.More for the catalytic active substance of auto-exhaust catalyst at present, and also routine techniques is belonged to for described those skilled in the art, therefore the application no longer repeats catalytic active substance at this.
The preparation process of above-mentioned catalyst support mainly comprises preparation primarily of Ti 3siC 2porous material and/or Ti 3alC 2the matrix that porous material is formed and by being oxidized the carrier layer prepared and be made up of in the oxide of matrix surface in-situ preparation to matrix, concrete technology route is as follows:
(1) mixed material is prepared: by TiH 2the mixed material of powder, Si powder and/or Al powder, graphite powder is placed in ball mill mixing and ball milling 3-12h, and containing mass fraction in mixed material is the TiH of 60-80wt% 2the graphite powder of the Si powder of powder, 5-35wt% and/or Al powder, 1-14wt%; A kind of be preferred embodiment make in mixed material containing mass fraction be the TiH of 72-75wt% 2the graphite powder of the Si powder of powder, 11-18wt% and/or Al powder, 10-14wt%, such proportioning can make the matrix finally obtained have performance better, such as large porosity and excellent mechanical property;
(2) granulation, drying and compression molding process: the mixed material of step (1) gained is carried out granulation, drying and compression molding successively, baking temperature is 40-80 DEG C, drying time is 4-12h, the pressure of compression molding is 150-250MPa, dwell time is 3-10 minute, obtains pressed compact after compression molding;
(3) sintering process of pressed compact: step (2) gained pressed compact is placed in sintering furnace and sinters, sintering process is carried out under vacuo, sintering process comprises following four-stage, first stage: sintering temperature rises to 400-450 DEG C from room temperature, heating rate is 1-25 DEG C/min, temperature retention time is 120-180min, and its effect removes moisture remaining in base substrate and granulating agent; Second stage: sintering temperature continued to rise to 600-700 DEG C, heating rate is 1-20 DEG C/min, and temperature retention time is 120-180min, and its effect promotes TiH 2dehydrogenation pore-creating; Phase III: sintering temperature is continued to rise to 900-1000 DEG C, heating rate is 1-20 DEG C/min, temperature retention time is 120-240min, and its effect facilitates Ti and C to react pore-creating to generate TiC phase, facilitates Ti and Al or Si reaction to generate compound between binary metal further simultaneously; Fourth stage: sintering temperature continued to rise to 1300 DEG C, heating rate is 1-10 DEG C/min, and temperature retention time is 180-300min, its effect promotes Ti 3siC 2and/or Ti 3alC 2the final synthesis of phase; After the temperature retention time of fourth stage terminates, namely sintering furnace obtains primarily of Ti after naturally cooling 3siC 2porous material and/or Ti 3alC 2the matrix that porous material is formed;
(4) in-situ oxidation process: the matrix of step (3) gained is placed in sintering furnace and sinters, the temperature of sintering is 400-600 DEG C, and heating rate is 1-20 DEG C/min, and sintering atmosphere is N 2and O 2gaseous mixture, temperature retention time is 2-6h, the catalyst support formed with the carrier layer that namely obtains being born in matrix surface by matrix and original position after stove cooling; By the controlled oxidization time, the oxide of different-grain diameter and the carrier layer of the different quality be made up of oxide and thickness can be obtained; Active force between the carrier layer that in-situ oxidation obtains and matrix is very strong, has evaded carrier layer in thump process and has come off so that catalyst forfeiture catalytic effect.
As the further improvement of the preparation method of catalyst support of the present invention, the sintering temperature of first stage is 450 DEG C, and the sintering temperature of second stage is 650 DEG C, and the sintering temperature of phase III is 1000 DEG C.
In the carrier layer of the catalyst support prepared by said method, the corresponding catalytic active substance of load, can obtain auto-exhaust catalyst.
Compared with prior art, because catalyst support has the performance of peer-level, therefore the auto-exhaust catalyst obtained after utilizing catalyst support supporting catalytic active component of the present invention has the clean-up effect of peer-level, but the carrier layer in the catalyst in the present invention be by the in-situ oxidation process of matrix in be born in carrier surface, therefore there is very strong adhesion between matrix and carrier layer, the shock resistance of carrier layer is strong, when thump, carrier layer difficult drop-off, thus the life-span significantly improving catalyst.
Detailed description of the invention
Below by the beneficial effect that detailed description of the invention is introduced enforcement of the present invention further and had.
For catalyst support of the application and preparation method thereof is described, prepared following 6 groups of experiments altogether, experiment 1 ~ 6 all belongs within the claimed scope of the application's claim.In order to the catalyst support prepared by the method for the application is described, the sample 1-6 that experiment 1-6 prepares is characterized.Specific as follows:
One, the preparation of mixture
The material composition of experiment 1-6 and content (in mass fraction) are in table 1.For ease of comparing, unified employing purity 99.7%, granularity-400 object TiH 2powder, purity 99.5%, granularity-325 object Si powder, the graphite powder of the Al powder of purity 99.5%, granularity 10-15 μm and purity 99.8%, granularity 5-6 μm.Certainly, in actual production, the aperture of the porous material that those skilled in the art also will be able to obtain according to it, adjusts targetedly to the particle diameter of each raw material.
Table 1: the composition that experiment 1-6 is raw materials used and content
Two, the ball milling of mixed material, granulation, drying, compression molding and sintering process
More even in order to make mixed material be mixed to get, reaction is more abundant, and need to carry out ball milling mixing to mixed material, the time of ball milling is 8 hours.After abundant mixing, consider the graphite powder being all mixed with lighter in weight in the raw material of experiment 1-6, easily cause segregation, therefore, also need to carry out granulation to the powder of experiment 1-6, carry out drying again after granulation, baking temperature is 60 DEG C, and drying time is 6 hours.Subsequently, loaded in the mould of unified specification by the dry mixed material of experiment 1-6 respectively, then these moulds are placed in cold isostatic compaction machine respectively, pressurize 5 minutes under 180MPa briquetting pressure, namely makes the cellular pressed compact being numbered 1-6 after the demoulding.Then, these pressed compacts are respectively charged into sintering boat, then these sintering boats are placed in sintering furnace sinter, with stove cooling after sintering, finally from each sintering boat, obtain matrix 1-6 again.
Prepare sintering process parameter that matrix 1-6 adopts in table 2, wherein, the unit of heating rate is DEG C/min, and the unit of sintering temperature is DEG C, and the unit of temperature retention time is minute.The sintering schedule of each experiment is divided into four-stage, carries out all under vacuo, and the effect of first stage removes moisture remaining in base substrate and granulating agent; The effect of second stage promotes TiH 2dehydrogenation pore-creating; The effect of phase III facilitates Ti and C to react pore-creating to generate TiC phase, facilitates Ti and Al or Si reaction to generate compound between binary metal further simultaneously; The effect of fourth stage promotes Ti 3siC 2and/or Ti 3alC 2the final synthesis of phase; After the temperature retention time of fourth stage terminates, sintering furnace naturally cools and namely obtains matrix 1-6.
Table 2: the sintering schedule of experiment 1-6
Three, in-situ oxidation process
The in-situ oxidation technological parameter of experiment 1-6 is in table 3, and wherein, the unit of heating rate is DEG C/min, and the unit of sintering temperature is DEG C, and the unit of temperature retention time is hour.Namely obtain catalyst support 1-6 after the in-situ oxidation process of experiment 1-6 completes, in catalyst support 1-6, be born in matrix surface in carrier layer, the adhesion between carrier layer and matrix is strong, solves the problem of catalyst support shock resistance difference.
Table 3: the in-situ oxidation process parameter of experiment 1-6
Four, the performance test of catalyst support
The performance test of catalyst support 1-6 is in table 4, and wherein, the unit of oxide average grain diameter is nm, and the unit of carrier layer content is mass fraction wt%, and the unit of support layer thickness is μm, and the unit of specific area is m 2/ g, the units MPa of tensile strength, the unit of thermal capacitance is J/kgK, and the unit of thermal conductivity is W/m DEG C.
The performance test results of table 4: catalyst support 1-6
As can be seen from Table 5, adopt the catalyst support 1-6 prepared by method of the application under the prerequisite that ensure that the strong adhesion between matrix and carrier layer, still there is excellent performance, its porosity>=35%, specific area>=25m 2/ g, tensile strength>=25MPa, normal temperature thermal conductivity>=26W/m DEG C, thermal capacitance≤600J/kgK.In general, the particle diameter of oxide is less, and the specific area of carrier layer is larger, can the catalytic active substance of load more.Along with the increase of supporter specific area, illustrate that the porosity of supporter promotes, but corresponding tensile strength also can reduce, for catalyst support of the present invention, due to porosity>=35%, so specific area>=25m 2/ g, but its tensile strength still can>=25MPa, not only can the more catalytic active substance of load, and there is very strong mechanical performance, in addition, thermal conductivity is the highest can reach 40W/m DEG C, can guarantee that catalytic process starts fast.
Four, dipping process
Supporting Pt/Rh/Pd in the coating of carrier surface can be born in experiment 1-6 obtains by simple infusion process, thus form vehicle tail gas triple effect catalyst 1-6.
Five, catalytic effect
Vehicle tail gas triple effect catalyst 1-6 in use, catalytic efficiency (CO) >=99%, catalytic efficiency (CH) >=99%, catalytic efficiency (NOx) >=99%; After use 30 days, catalytic efficiency still can keep more than 95% of initial catalyst efficiency, and traditional be that the catalytic efficiency of the vehicle tail gas triple effect catalyst of matrix declines rapidly with cordierite, after use 30 days, catalytic efficiency (CO)≤85%, catalytic efficiency (CH)≤80%, catalytic efficiency (NOx)≤90%.
To sum up, vehicle tail gas triple effect catalyst of the present invention has excellent and stable catalytic efficiency, this gives the credit to its good structural stability, illustrate that the adhesion in supporter between carrier layer and matrix is strong, make supporter have excellent shock resistance, thus extend the life-span of vehicle tail gas triple effect catalyst.

Claims (9)

1. catalyst support, comprise matrix and be attached to the carrier layer on matrix, it is characterized in that, described matrix is primarily of Ti 3siC 2porous material and/or Ti 3alC 2porous material is formed; Described carrier layer is by be oxidized matrix thus in-situ preparation is formed in the oxide of carrier surface; Described oxide comprises TiO 2or comprise Al 2o 3and SiO 2in at least one and TiO 2mixture.
2. catalyst support according to claim 1, is characterized in that, the average grain diameter of described oxide is 100-200nm, and the thickness of carrier layer is 50-200 μm, and the quality of carrier layer accounts for the 0.2-0.5% of supporter quality.
3. catalyst support according to claim 1, is characterized in that, the thickness of carrier layer is 150-200 μm, and the quality of carrier layer accounts for the 0.35-0.5% of supporter quality.
4. according to the catalyst support in claim 1-3 described in any one, it is characterized in that, porosity>=35% of catalyst support, specific area>=25m 2/ g, tensile strength>=25MPa, thermal conductivity>=26W/m DEG C, thermal capacitance≤600J/kgK.
5. the application of the catalyst support described in claim 1-4 any one in auto-exhaust catalyst.
6. the method for Kaolinite Preparation of Catalyst supporter, is characterized in that, preparation process mainly comprises preparation primarily of Ti 3siC 2porous material and/or Ti 3alC 2the matrix that porous material is formed and by being oxidized the carrier layer prepared and be made up of in the oxide of matrix surface in-situ preparation to matrix, concrete technology route is as follows:
(1) mixed material is prepared: by TiH 2the mixed material of powder, Si powder and/or Al powder, graphite powder is placed in ball mill mixing and ball milling 3-12h, and containing mass fraction in mixed material is the TiH of 60-80wt% 2the graphite powder of the Si powder of powder, 5-35wt% and/or Al powder, 1-14wt%;
(2) granulation, drying and compression molding process: the mixed material of step (1) gained is carried out granulation, drying and compression molding successively, baking temperature is 40-80 DEG C, drying time is 4-12h, the pressure of compression molding is 150-250MPa, dwell time is 3-10 minute, obtains pressed compact after compression molding;
(3) sintering process of pressed compact: step (2) gained pressed compact is placed in sintering furnace and sinters, sintering process is carried out under vacuo, sintering process comprises following four-stage, first stage: sintering temperature rises to 400-450 DEG C from room temperature, heating rate is 1-25 DEG C/min, and temperature retention time is 120-180min; Second stage: sintering temperature is continued to rise to 600-700 DEG C, heating rate is 1-20 DEG C/min, and temperature retention time is 120-180min; Phase III: sintering temperature continued to rise to 900-1000 DEG C, heating rate is 1-20 DEG C/min, and temperature retention time is 120-240min; Fourth stage: sintering temperature continued to rise to 1300 DEG C, heating rate is 1-10 DEG C/min, and temperature retention time is 180-300min; After the temperature retention time of fourth stage terminates, namely sintering furnace obtains primarily of Ti after naturally cooling 3siC 2porous material and/or Ti 3alC 2the matrix that porous material is formed;
(4) in-situ oxidation process: the matrix of step (3) gained is placed in sintering furnace and sinters, the temperature of sintering is 400-600 DEG C, and heating rate is 1-20 DEG C/min, and sintering atmosphere is N 2and O 2gaseous mixture, temperature retention time is 2-6h, the catalyst support formed with the carrier layer that namely obtains being born in matrix surface by matrix and original position after stove cooling.
7. the method for Kaolinite Preparation of Catalyst supporter according to claim 6, is characterized in that, containing mass fraction in mixed material in step (1) is the TiH of 72-75wt% 2the graphite powder of the Si powder of powder, 11-18wt% and/or Al powder, 10-14wt%.
8. the method for Kaolinite Preparation of Catalyst supporter according to claim 6, is characterized in that, in step (3), the sintering temperature of first stage is 450 DEG C, and the sintering temperature of second stage is 650 DEG C, and the sintering temperature of phase III is 1000 DEG C.
9. the preparation method of auto-exhaust catalyst, is included in the supporting layer supports catalytic active substance of the catalyst support described in claim 1-8 any one.
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CN106902809A (en) * 2017-04-12 2017-06-30 湖南云平环保科技有限公司 Reproducible SCR catalyst and preparation method thereof
CN106914252A (en) * 2017-03-02 2017-07-04 湖南云平环保科技有限公司 Porous material is SCR catalyst of carrier and preparation method thereof between TiFeAl metals

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Publication number Priority date Publication date Assignee Title
CN106914252A (en) * 2017-03-02 2017-07-04 湖南云平环保科技有限公司 Porous material is SCR catalyst of carrier and preparation method thereof between TiFeAl metals
CN106914252B (en) * 2017-03-02 2019-06-04 江苏新沃催化剂有限公司 Porous material is the SCR catalyst and preparation method thereof of carrier between TiFeAl metal
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CN106902841B (en) * 2017-03-14 2019-07-26 湖南云平环保科技有限公司 Porous material supporter and preparation method thereof between TiFe metal
CN106902809A (en) * 2017-04-12 2017-06-30 湖南云平环保科技有限公司 Reproducible SCR catalyst and preparation method thereof
CN106902809B (en) * 2017-04-12 2019-08-27 台州三元车辆净化器有限公司 Reproducible SCR catalyst and preparation method thereof

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