CN104774002B

CN104774002B - Porous cordierite with catalytic activity and preparation method of porous cordierite

Info

Publication number: CN104774002B
Application number: CN201510158376.XA
Authority: CN
Inventors: 柳斌
Original assignee: Jiangxi An Tian New High-Tech Material Co Ltd
Current assignee: Jiangxi Antan high tech Material Co.,Ltd.
Priority date: 2015-04-03
Filing date: 2015-04-03
Publication date: 2017-02-22
Anticipated expiration: 2035-04-03
Also published as: CN104774002A

Abstract

The invention relates to porous cordierite with catalytic activity and a preparation method of the porous cordierite. The porous cordierite comprises the following components in percentage by mass: 36.6% of talc, 43.1% of kaolin, 14.1% of aluminum oxide, 5.6% of carbon containing diatomite based on diatomite, 0.2% of La2Ce2O7, 0.3% of BaNb2O6 and 0.1% of BaTiO3. The preparation method comprises the following steps: mixing and grinding the raw materials and drying for 10 hours at 110 DEG C; then raising the temperature at a speed of 1 DEG C/minute to 800 DEG C in a nitrogen atmosphere and insulating for 5 hours; and then further raising the temperature at a speed of 1 DEG C/minute to 1350 DEG C in an air atmosphere and insulating for 10 hours. The cordierite is high in specific surface and low in coefficient of thermal expansion and has the catalytic activity.

Description

A kind of have porous cordierite of catalysis activity and preparation method thereof

Technical field

The present invention relates to catalyst carrier technical field and in particular to a kind of porous cordierite with catalysis activity and its Preparation method.

Background technology

With while economic development, current environment and energy shortage problem increasingly receive publicity.As adopted gasoline With the automobile of diesel oil, need to install additional catalyst exhaust purifier and carry out in cleaning of off-gas the poisonous and hazardous pollutant to human body.A lot The harmful substance of chemical industry discharge is also required to be acted upon by catalyst.And making the indispensable carrier of catalyst is violet The honeycomb substrate that cordierite material is fired, cordierite has that thermal coefficient of expansion is low, the high feature of the porosity.Blue or green just because of violet Stone material has excellent thermal shock resistance, is widely used in the field such as catalyst field and heat-storing material.

Due to natural cordierite seldom, industrial all prepare cordierite using artificial synthesis.Due to adopting cordierite In corresponding pure-oxide come synthesis of high purity cordierite cost of material high, firing temperature is high, firing temperature window narrows, lead to The cost of high-purity cordierite is very high, industrial cannot large-scale promotion use.Therefore, adopt conjunction based on natural material at present more Become cordierite, such as using natural materials such as Talcum, Kaolin.Synthesize field in cordierite material, if the heat reducing material is swollen Swollen coefficient is an important index, reduces thermal coefficient of expansion in addition to synthesis technique, depends primarily on the method adding auxiliary agent. Further, since cordierite material is mainly used in purifying vehicle exhaust, industrial organic exhaust gas process field, if in cordierite material Add auxiliary agent in building-up process, not only can reduce the thermal coefficient of expansion of material, there is certain catalytic performance again, will significantly expand The application of cordierite material.

Content of the invention

The technical problem to be solved in the present invention is that offer is a kind of has porous cordierite of catalysis activity and preparation method thereof.

For solving above-mentioned technical problem, the technical solution used in the present invention is：

A kind of porous cordierite with catalysis activity, this cordierite by Talcum, Kaolin, aluminium oxide, carbon containing kieselguhr, La₂Ce₂O₇、BaNb₂O₆And BaTiO₃Form, the weight/mass percentage composition of each composition is：Talcum 36.6%；Kaolin 43.1%；Oxygen Change aluminum 14.1%；Carbon containing kieselguhr 5.6% with kieselguhr metering；La₂Ce₂O₇0.2%；BaNb₂O₆0.3%； BaTiO₃0.1%.

By raw material according to weight/mass percentage composition：Talcum 36.6%；Kaolin 43.1%；Aluminium oxide 14.1%；Carbon containing diatom Native (in terms of kieselguhr) 5.6%；La₂Ce₂O₇0.2%；BaNb₂O₆0.3%；BaTiO₃0.1%, 110 DEG C after mixing, grinding Dry 10 hours, then with 1 DEG C per minute of heating rate, be warmed up to 800 DEG C in a nitrogen atmosphere, be incubated 5 hours, then switch Become air atmosphere, continue with 1 DEG C per minute of heating rate, be warmed up to 1350 DEG C, insulation is burnt till for 10 hours.

The diatomaceous preparation method of described carbon containing selects SiO for kieselguhr₂The high purity silicon diatomaceous earth essence that content is more than 90% Soil, according to sucrose:Kieselguhr mass ratio=1:2, weigh corresponding sucrose and kieselguhr, the sucrose water dissolution of twice quality, Then mix with kieselguhr, after 2 hours, evaporation at 100 DEG C removes moisture to dipping, then little in 500 DEG C of nitrogen atmosphere roastings 4 When.

Described La₂Ce₂O₇Preparation method：It is 1 according to La and Ce mol ratio, weigh corresponding La₂O₃With Ce (CO₃)₂, mix Grind after conjunction, then in 1400 DEG C of air atmosphere roastings 8 hours.

Described BaNb₂O₆Preparation method：It is 1 according to Ba and Nb mol ratio, weigh corresponding BaCO₃And Nb₂O₅, after mixing Grind, then in 1000 DEG C of air atmosphere roastings 8 hours.

Described BaTiO₃Preparation method：It is 1 according to Ba and Ti mol ratio, weigh corresponding BaCO₃And TiO₂, after mixing Grind, then in 1000 DEG C of air atmosphere roastings 8 hours.

Cordierite material is mainly used in purifying vehicle exhaust, the catalyst carrier of industrial organic exhaust gas process field, if Cordierite material has certain catalysis activity, plays help to the performance improving load active component rear catalyst.This The adjustment by cordierite synthesizing formula for the invention, to reduce the thermal coefficient of expansion of material, and makes cordierite material have in itself Catalysis activity.The cordierite specific surface being obtained using preparation method of the present invention is high, thermal coefficient of expansion is low, have catalysis simultaneously lives Property.

Specific embodiment

With reference to embodiment, the present invention is made and further illustrating, but the present invention is not limited to these enforcements Example.

Embodiment 1

(1) the diatomaceous preparation of carbon containing：Kieselguhr selects SiO₂The high purity silicon diatomaceous earth essence soil that content is more than 90%, according to Quality compares sucrose:Kieselguhr=1:2, weigh corresponding sucrose and kieselguhr.The sucrose water dissolution of twice quality, then with silicon Diatomaceous earth mixes, and after 2 hours, evaporation at 100 DEG C removes moisture, then in 500 DEG C of nitrogen atmosphere roastings 4 hours, sucrose to dipping Through carbonization, generate carbon containing kieselguhr.

(2)La₂Ce₂O₇Preparation：It is 1 according to La and Ce mol ratio, weigh corresponding La₂O₃With Ce (CO₃)₂, after mixing Grind, then in 1400 DEG C of air atmosphere roastings 8 hours.

(3)BaNb₂O₆Preparation：It is 1 according to Ba and Nb mol ratio, weigh corresponding BaCO₃And Nb₂O₅, grind after mixing, Then in 1000 DEG C of air atmosphere roastings 8 hours.

(4)BaTiO₃Preparation：It is 1 according to Ba and Ti mol ratio, weigh corresponding BaCO₃And TiO₂, grind after mixing, Then in 1000 DEG C of air atmosphere roastings 8 hours.

(5) with selected Talcum, selected Kaolin, aluminium oxide, carbon containing kieselguhr, La₂Ce₂O₇、BaNb₂O₆And BaTiO₃For former Material.Raw material is according to following mass percent：Selected Talcum 36.6%；Selected Kaolin 43.1%；Aluminium oxide 14.1%；Carbon containing silicon Diatomaceous earth (in terms of kieselguhr) 5.6%；La₂Ce₂O₇0.2%；BaNb₂O₆0.3%；BaTiO₃0.1%.Above raw material process mixing, Compressing after grinding, dried 10 hours with 110 DEG C, then with 1 DEG C per minute of heating rate, be warmed up in a nitrogen atmosphere 800 DEG C, it is incubated 5 hours, then switches to air atmosphere, continue with 1 DEG C per minute of heating rate, be warmed up to 1350 DEG C, protect Temperature is burnt till for 10 hours.

(6) specific surface area of sample to be measured using the BET method of nitrogen adsorption under liquid nitrogen temperature, the results are shown in Table 1.

(7) sample MEASURING THE THERMAL EXPANSION COEFFICIENT, to cordierite sample after grinding, carries out heat swollen in the range of 50-800 DEG C Swollen coefficient determination, the results are shown in Table 1.

(8) catalytic performance test of sample, to cordierite sample broke, selects 20～40 mesh cordierite 2ml, is attached to catalysis In reactor.Using propane combustion reaction as simulation reaction, Propane-air is reacting gas, and propane concentration is 1000ppm, leads to Cross catalyst, reaction gas flow is 670ml/min.The conversion ratio of propane at a temperature of analytical reactions.The results are shown in Table 1.

Comparative example 1

(1) with selected Talcum, selected Kaolin, aluminium oxide, Primary Study of Choosing Diatomite as raw material.Raw material is according to following percent mass Number：Selected Talcum 36.9%；Selected Kaolin 43.4%；Aluminium oxide 14.1%；Primary Study of Choosing Diatomite 5.6%.Above raw material passes through Compressing after mixing, grinding, dried 10 hours with 110 DEG C, then with 1 DEG C per minute of heating rate, rise in a nitrogen atmosphere Temperature, to 800 DEG C, is incubated 5 hours, then switches to air atmosphere, continues with 1 DEG C per minute of heating rate, is warmed up to 1350 DEG C, insulation is burnt till for 10 hours.

(2) sample MEASURING THE THERMAL EXPANSION COEFFICIENT and catalytic performance test are same as Example 1, the results are shown in Table 1.

The thermal coefficient of expansion of table 1 embodiment and comparative example's catalyst and catalytic performance

As can be seen here, the cordierite material of the present invention has the characteristics that thermal coefficient of expansion is low and has oxidation activity to propane.

Claims

1. a kind of porous cordierite with catalysis activity it is characterised in that：This cordierite by Talcum, Kaolin, aluminium oxide, contain Carbon kieselguhr, La₂Ce₂O₇、BaNb₂O₆And BaTiO₃Form, the weight/mass percentage composition of each composition is：Talcum 36.6%, Kaolin 43.1%, aluminium oxide 14.1%, with the carbon containing kieselguhr 5.6% of kieselguhr metering, La₂Ce₂O₇0.2%, BaNb₂O₆0.3%, BaTiO₃0.1%.

2. porous cordierite according to claim 1 is it is characterised in that the diatomaceous preparation method of described carbon containing is diatom Soil selects SiO₂The high purity silicon diatomaceous earth essence soil that content is more than 90%, according to sucrose:Kieselguhr mass ratio=1:2, weigh corresponding Sucrose and kieselguhr, the sucrose water dissolution of twice quality, then mix with kieselguhr, dipping 2 hours after, at 100 DEG C Evaporation removes moisture, then in 500 DEG C of nitrogen atmosphere roastings 4 hours.

3. porous cordierite according to claim 1 is it is characterised in that described La₂Ce₂O₇Preparation method：According to La with Ce mol ratio is 1, weighs corresponding La₂O₃With Ce (CO₃)₂, grind after mixing, then little in 1400 DEG C of air atmosphere roastings 8 When.

4. porous cordierite according to claim 1 is it is characterised in that described BaNb₂O₆Preparation method：According to Ba and Nb Mol ratio is 1, weighs corresponding BaCO₃And Nb₂O₅, grind after mixing, then in 1000 DEG C of air atmosphere roastings 8 hours.

5. porous cordierite according to claim 1 is it is characterised in that described BaTiO₃Preparation method：According to Ba and Ti Mol ratio is 1, weighs corresponding BaCO₃And TiO₂, grind after mixing, then in 1000 DEG C of air atmosphere roastings 8 hours.

6. a kind of preparation method of the porous cordierite catalyst with catalysis activity is it is characterised in that by raw material according to quality hundred Divide content：Talcum 36.6%, Kaolin 43.1%, aluminium oxide 14.1%, with the carbon containing kieselguhr 5.6% of kieselguhr metering, La₂Ce₂O₇0.2%, BaNb₂O₆0.3%, BaTiO₃After 0.1% mixing, grinding, dry 10 hours through 110 DEG C, then with every point The heating rate that 1 DEG C of clock, is warmed up to 800 DEG C in a nitrogen atmosphere, is incubated 5 hours, then switches to air atmosphere, continues with every The heating rate of 1 DEG C of minute, is warmed up to 1350 DEG C, and insulation is burnt till for 10 hours.