CN105399406A - Exhaust purifier for automobile and preparation method of exhaust purifier - Google Patents
Exhaust purifier for automobile and preparation method of exhaust purifier Download PDFInfo
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- CN105399406A CN105399406A CN201510800082.2A CN201510800082A CN105399406A CN 105399406 A CN105399406 A CN 105399406A CN 201510800082 A CN201510800082 A CN 201510800082A CN 105399406 A CN105399406 A CN 105399406A
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Abstract
The invention discloses an exhaust purifier for an automobile and a preparation method of the exhaust purifier. The exhaust purifier for the automobile comprises a casing and a honeycomb ceramic carrier, wherein the honeycomb ceramic carrier is arranged in the casing; a porous structure of the honeycomb ceramic carrier comprises bent S-shaped channels and straight channels communicated to the S-shaped channels; the honeycomb ceramic carrier comprises components in percentage by mass as follows: 10%-15% of a sintering aid, 4%-10% of titanium nitride, 2%-5% of a dispersion agent, 2%-5% of rare-earth oxide, 1%-2% of reinforced fibers and the balance of aluminum oxide powder. The grain size of aluminum oxide is reduced, and titanium nitride, the dispersion agent, the rare-earth oxide and the reinforced fibers are added, so that the carrier has high compressive strength, low thermal expansion coefficient and higher heat-conducting property and cooling performance; the preparation method is simple, efficient and applicable to large-scale production of the exhaust purifier for the automobile.
Description
Technical field
The present invention relates to purifying vehicle exhaust gas field, especially a kind of vehicle tail gas purification device and preparation method thereof.
Background technology
Along with becoming increasingly conspicuous of air pollution problems inherent and increasing sharply of automobile quantity, waste gas one of primary pollution source becoming urban air pollution of motor vehicle emission.Objectionable impurities in vehicle exhaust mainly contains CO, NOx and HC, polycyclic aromatic hydrocarbons (PAH) and suspended substance (SPM) etc.NOx and HC, in an atmosphere through a series of photochemical reaction, easily generates the very strong material of the multiple oxidisability such as ozone, forms photo-chemical smog.The health of photo-chemical smog not only serious harm people, and can do great damage to animals and plants and various material.
Vehicle tail gas purification device, is mounted in most important outer purifier in automobile exhaust system, and the obnoxious flavoures such as CO, HC and NOx that vehicle exhaust can be discharged by it change harmless carbonic acid gas, water and nitrogen into by oxidation and reductive action.When the vehicle exhaust of high temperature is by refining plant, scavenging agent in exhaust purifier will strengthen the activity of CO, HC and NOx tri-kinds of gases, impel it to carry out certain oxidation-reduction chemical reaction, wherein CO is at high temperature oxidized into colourless, nontoxic carbon dioxide; HC compound is at high temperature oxidized to water (H
20) and carbonic acid gas; NOx is reduced into nitrogen and oxygen.Three kinds of obnoxious flavoures become innocuous gas, and vehicle exhaust is purified.
Exhaust purifier comprises housing, carrier and is covered in the catalyzer of carrier surface.Early stage carrier many employings particulate vector, but due to the catalyzer of particulate vector have that packing density is large, bed resistance large, the easy shortcoming such as pulverizing, be unsuitable for purifying vehicle exhaust.And the passage of cellular monolithic catalytic agent carrier owing to having longitudinally, continuously, not stopped, the advantages such as resistance of exhaust is little, are widely used in the purification of vehicle exhaust, this kind of carrier of the many employings of current auto-exhaust catalyst in research afterwards.Early 1970s, 3M company and Ford's sintering process produce a kind of honeycomb ceramic carrier, within 1972, Corning Incorporated also develops a kind of honeycomb ceramic carrier, within 1986, Corning Incorporated produces honeycomb ceramic carrier at West Germany's instrument factory, to meet the needs of European car industry, the large-scale promotion for automotive catalyst has established solid basic substance.China greatly about 20th century the mid-80 start to produce honeycomb ceramic carrier, although have passed through the development of more than ten years, due to the reason such as technology, equipment, compared with external product, also have a certain distance.
Ceramic monolith is now widely used catalyst carrier for purifying vehicle tail gas, wherein more commonly CORDIERITE HONEYCOMB CERAMIC CARRIER.Industrialized cordierite ceramic preparation method is raw material mainly with kaolin, talcum or pure component oxide compound, adopts high temperature solid state reaction synthesis.It is simple that the method has production technique, production efficiency advantages of higher; But its greatest problem existed is exactly that synthesis temperature is high, and energy consumption is large, and sintering temperature reaches 1390 ~ 1400 DEG C, and its sintering warm area is very narrow.As introduced glassy phase, suitably can reduce the sintering temperature of cordierite ceramic, widening its sintering warm area, but improve its thermal expansivity, reducing the ability of anti-thermal shock and erosion.Precipition wrapping method and sol-gel method craft require relatively stricter, and building-up process is complicated, and raw material mostly is organic compound, expensive, and some is also harmful, is difficult to meet industrial application requirement.
Add auxiliary agent in utilization and improve cordierite ceramic aspect of performance, auxiliary agent mostly is single constituent element, often mean thermal expansion coefficients is very little, but there is larger difference in the thermal expansivity of its a axle and c-axis, be difficult to " zero thermal expansion " and Anisotropically heat effects are coordinated mutually, thus reduce the thermal characteristics of cordierite ceramic.
Aluminum oxide is also a kind of common stupalith, there is many excellent performances such as high temperature resistant, wear-resisting, corrosion-resistant, anti-oxidant, but because aluminum oxide self cationic charge is many, the features such as radius is little, and ionic linkage is strong, cause its lattice energy larger, spread coefficient is lower, sintering temperature is high, also receives certain restriction because the defect that its fragility is large, thermal expansivity is high makes it apply in addition, therefore needs a kind of effective ways that can solve the problem of searching badly.
Summary of the invention
For solving the problem, the invention discloses a kind of vehicle tail gas purification device and preparation method thereof, the carrier of this purification agent for treating waste gas take aluminum oxide as matrix, adds the carrier that sintering aid, titanium nitride, dispersion agent, rare earth oxide and strongthener make to obtain and have high compressive strength, lower thermal expansivity and higher heat conductivility and heat dispersion.
Technical scheme of the present invention is: a kind of vehicle tail gas purification device, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is fixed in housing, and the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of described honeycomb ceramic carrier comprise: sintering aid: 10-15%, titanium nitride: 4-10%, dispersion agent: 2-5%, rare earth oxide: 2-5%, fortifying fibre: 1-2%, surplus is alumina powder jointed.(wherein straight way is communicated to carrier surface, and serpentine channel is arranged on carrier inside, so arranges the intake resistance that can reduce carrier surface, thus raising high-speed and high-temperature tail gas enters the efficiency that carrier carries out purifying)
Preferred as one, the open porosity of described honeycomb ceramic carrier is 70-80%.The heat conductivility of open porosity on honeycomb ceramic carrier has larger impact, the equivalent diameter of high opening rate ceramic honey comb is greater than low percentage of open area ceramic honey comb equivalent diameter, like this, under same volume, the ceramic honey comb with the open porosity of 70-80% has larger hole inner area, time temperature is higher, radiative transfer increase is faster, and effective thermal conductivity is raised fast.
Preferred as one, the pore volume of described straight way and serpentine channel is than being (7-8): (4-5).At the serpentine channel that the inner setting unit of ceramic monolith is bending, and be communicated with straight way, make exhaust gas flow, through connectivity part formation eddy current or turbulent flow, irregular mixing occur, play the effect of stirring, serpentine channel too increases contact area and the contact pressure of tail gas and channel surface catalyzer simultaneously, effectively improves catalytic efficiency.When the pore volume ratio of straight way and serpentine channel is (7-8): time (4-5), control straight way volume and be greater than serpentine channel volume, the intake resistance of tail gas is not too large, also can not exceed cracking limit with the contact pressure of hole wall, is conducive to carrying out smoothly of tail gas clean-up.
Preferred as one, alumina powder jointed particle diameter is 150-200nm.Common aluminum oxide ceramics often needs higher sintering temperature and adds its application cost in exhaust purifier.Because sintering is the migration being realized material by surface tension, therefore need higher activation energy, and the alumina ceramic grain particle diameter of refinement is little, specific surface area is large, surfactivity is high, the distance of interparticle diffusion is short, only need lower sintering activating energy and sintering temperature, obviously can improve the physicals of ceramic body, demonstrate excellent mechanical property.
Preferred as one, sintering aid is MgO, CaO, SiO
2, V
2o
5, Fe
2o
3, TiO
2in at least two kinds.Multiple sintering aid add thermal expansivity and the sintering temperature that effectively can reduce alumina ceramic material, improve sintering character, because the surface energy of nanometer alumina powder particle is larger, in the process of high temperature sintering densification, the easy ramp of crystal grain affects material mechanical performance, and in alumina-ceramic coating, add sintering aid, its crystal grain can be suppressed to grow up when high temperature on the one hand, on the other hand, also can reduce its sintering temperature.
Add the rare earth oxide of 2-5%, such as lanthanum trioxide, cerium oxide, Praseodymium trioxide, all obviously can improve microstructure and the performance of alumina ceramic material, wherein lanthanum, cerium, praseodymium element are surface active elements, when its oxide particle and blapharoplast meet, tend to be distributed in blapharoplast surface, the impurity of absorption grain boundaries, purification crystal boundary.Rare earth oxide particles and alumina particle contact reacts form low melting point liquid phase in addition, obviously can reduce the sintering temperature of pottery.When rare earth oxide content lower than 2% time, sintering temperature reduces not obvious, affect the surfactivity of cleaner, and content higher than 5% time, porosity can be caused greatly to reduce, and be unfavorable for the specific surface area of increase stupalith, therefore its content there is no need to be greater than 5%.
Preferred as one, the mass ratio of titanium nitride and rare earth oxide is (3-5): 2.Titanium nitride plays good conductive force in Extruded Monolithic Celluar Ceramics of the present invention, and higher heat conductivility scatters heat energy come in larger region, and avoid producing defect because of thermal stresses, after being heated, radiating rate also can be fast especially; In the practical application of vehicle tail gas purification device, the good honeycomb ceramic carrier of thermal conductivity is when being subject to tail gas and impacting, can absorb quickly and transmit the heat of tail gas, the sufficient heat needed for deactivated catalyst is provided equably to carrier, especially, when low temperature, the catalyzer of carrier surface can start catalyst mechanism quickly.Under the acting in conjunction of sintering aid and rare earth oxide, the fusing point of titanium nitride can obviously reduce; When the mass ratio of titanium nitride and rare earth oxide is (3-5): when 2, the thermal conductivity of stupalith can improve greatly.This is because titanium nitride and rare earth oxide are easy to form melting behaviors at ceramic grain-boundary place at high temperature, oxygen impurities is adsorbed on crystal boundary, decrease the possibility that oxygen impurities enters lattice, the oxygen of intracell also can reduce and the spontaneous grain boundaries that is diffused into because of the oxygen concn of grain boundaries greatly, the oxygen level of ceramic lattice is reduced, and the value volume and range of product of ceramic structure defect reduces, thus reduces phon scattering probability, increase the mean free path of phonon, promote thermal conductivity.
Preferred as one, dispersion agent comprises water glass, glycerine, carboxymethyl cellulose, stearic acid.In ceramic matrix, add dispersion agent can make ceramic matrix powder not be separated with other additive Homogeneous phase mixing, the dispersion agent formed by water glass, glycerine, carboxymethyl cellulose, stearic acid and ceramic powder wetting angle little, there is good affinity.Wherein glycerine can produce good flow characteristics, can soak powder well, the adhesive attraction that water glass is effectively good to ceramic powder.In order to improve the wettability of dispersion agent, therefore add stearic acid and carboxymethyl cellulose, they produce intermediate interface bridge between ceramic powder and dispersion agent, add certain mobility.Meanwhile, dispersion agent to produce capillary force adsorption particle, keeps base substrate indeformable by wet granulate.
Preferred as one, dispersion agent mesosilicic acid sodium, glycerine, carboxymethyl cellulose, stearic mass ratio are (3-5): (7-9): (1-3): 1.When water glass, glycerine, carboxymethyl cellulose, stearic mass ratio are (3-5): (7-9): (1-3): when 1, dispersing property and the adhesive property of dispersion agent reach a kind of more harmonious balance, not only can realize effective dispersion, cohesiveness can not be made again too low and lose the effect adhering to ceramic powder, wherein the quality control of carboxymethyl cellulose is in this ratio, can avoid, because of the fusing of ceramic composition high-temperature heating, occurring swelling and causing blank cracking when carboxymethyl cellulose dissolves.
Preferred as one, fortifying fibre is the one in silicon carbide fiber or carbon fiber.Due to the Embrittlement of stupalith, make stupalith at high temperature, heavily stressed, the application particularly under dynamic condition is restricted.And silicon carbide fiber and carbon fiber strength is high, modulus is high, density is low, stable chemical performance, thermal expansivity are little, there is good high thermal resistance, be subject in the process of foreign impacts at stupalith, silicon carbide fiber and carbon fiber can change crackle the evolving path, absorb energy to fracture, the connection transboundary to different crystal boundary, crystallizing field and impurity defect region can also be realized, thus reach the object improving stupalith fragility, intensified ceramic material.Described fortifying fibre is through plasma surface pretreated.Silicon carbide fiber and carbon fiber surface inertia larger, poor with the consistency of ceramic matrix, easily on interface, form hole and defect, cause with the bonding strength at interface lower.Use Cement Composite Treated by Plasma mainly by plasma strike fiber surface, thus etching fiber sheath, the roughness on its surface is increased, and surface-area is corresponding increase also, significantly increases so the wetting property of fiber in ceramic matrix has; Cement Composite Treated by Plasma silicon carbide fiber and carbon fiber can make its degree of graphitization and regularity reduce simultaneously, increase, so cohesiveness also increases with the mechanical twisting point of ceramic matrix; Cement Composite Treated by Plasma also can form radical at fiber surface, improves interface binding power, improves mechanical property.
A preparation method for vehicle tail gas purification device, comprises the steps:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, by mixed powder with water with (80-85): the mass ratio of 100 fully mixes, add dispersion agent and fortifying fibre again, be uniformly dispersed and obtain ceramic size;
2) shaping base, obtains biscuit; Being embodied as step 1 of this step) gained slurry undertaken by extrusion equipment;
3) sinter: biscuit regulates pressure to 20MPa in 1100-1200 DEG C of sintering 60-90min, b. by a. at ambient pressure, adjust the temperature to 900-1100 DEG C of continuation sintering 30-60min, c. and be incubated 90-120min at 500-700 DEG C, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again;
5) subsequent disposal: by step 4) the carrier drying that obtains and calcination process (put into stoving oven and carry out adding thermal bake-out by following temperature curve, time controling is at 5-8h: one district: 170-190 DEG C, 2nd district: 200-240 DEG C, 3rd district: 280-320 DEG C, 4th district: 370-500 DEG C, 5th district: 500-520 DEG C) after carrier and housing are assembled, make complete vehicle tail gas purification device.Carrier carries out adding thermal bake-out according to temperature curve, carrier is heated and compares uniform speed slow, moisture can be removed equably, temperature distributing disproportionation can not be caused to make active coating ftracture or come off because heating up suddenly, it also avoid the deformation and damage of base substrate in roasting process simultaneously, and in this temperature profile range, the components such as palladium, platinum, rhodium also can keep maximum activity can not inactivation.
Described step 4) coating is divided into and completes for twice, and wherein the wet weightening finish of second time coating is than first time heavy 45-55% (coating here wet weightening finish refer to the increasing amount of carrier quality after coating).
Described step 4) coating after carrier percentage of plugged hole be less than 1%.If there is plug-hole phenomenon, be then less than 1% (number in hole that percentage of plugged hole is here blocked after referring to carrier coating and the ratio of total hole count) with air gun purging to percentage of plugged hole.
Beneficial effect of the present invention: adopt the vehicle tail gas purification device that technique scheme is obtained; its honeycomb ceramic carrier ultimate compression strength is high, thermal expansivity is little, sintering temperature is low; there is higher heat conductivility and heat dispersion; be applicable to the application in tail gas clean-up field; its preparation method is simply efficient, is applicable to large-scale production.
Embodiment
Below in conjunction with embodiment, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
Vehicle tail gas purification device disclosed by the invention, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is arranged in housing, and the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of described honeycomb ceramic carrier comprise: sintering aid: 10-15%, titanium nitride: 4-10%, dispersion agent: 2-5%, rare earth oxide: 2-5%, fortifying fibre: 1-2%, surplus is alumina powder jointed.
Preferred as one, the open porosity of described honeycomb ceramic carrier is 70-80%.
Preferred as one, the pore volume of described straight way and serpentine channel is than being (7-8): (4-5).
Preferred as one, described alumina powder jointed particle diameter is 150-200nm.
Preferred as one, described sintering aid is MgO, CaO, SiO
2, V
2o
5, Fe
2o
3, TiO
2in at least two kinds.
Preferred as one, the mass ratio of described titanium nitride and rare earth oxide is (3-5): 2.
Preferred as one, dispersion agent comprises water glass, glycerine, carboxymethyl cellulose, stearic acid.
Preferred as one, dispersion agent mesosilicic acid sodium, glycerine, carboxymethyl cellulose, stearic mass ratio are (3-5): (7-9): (1-3): 1.
Preferred as one, described fortifying fibre is the one in silicon carbide fiber or carbon fiber.
The preparation method of vehicle tail gas purification device of the present invention, comprises the steps:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, by mixed powder with water with (80-85): the mass ratio of 100 fully mixes, add dispersion agent and fortifying fibre again, be uniformly dispersed and obtain ceramic size;
2) shaping base, obtains biscuit;
3) sinter: after biscuit is sintered 60-90min in 1100-1200 DEG C by a. at ambient pressure, b. regulate pressure to 20MPa, adjust the temperature to 900-1100 DEG C of continuation sintering 30-60min, c. and at 500-700 DEG C, be incubated 90-120min again, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again;
5) subsequent disposal: by step 4) assemble with housing after the carrier drying that obtains and calcination process, make vehicle tail gas purification device.
Embodiment 1
The vehicle tail gas purification device of the present embodiment, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is arranged in housing, and the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of honeycomb ceramic carrier comprise: sintering aid: 12%, titanium nitride: 4%, dispersion agent: 4%, rare earth oxide: 5%, silicon carbide fiber: 2%, all the other are alumina powder jointed.Wherein MgO and CaO of sintering aid to be mass ratio be 1:1, dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide; Wherein silicon carbide fiber is (this place pretreating scheme can also be applicable to include, without being limited to the present invention and enumerate other embodiment in interior all technical schemes) through argon plasma surface preparation.Wherein the open porosity of ceramic honey comb is 75%, and straight way is 7:5 with the pore volume ratio of serpentine channel.
Embodiment 2
The vehicle tail gas purification device of the present embodiment, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is arranged in housing, and the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of honeycomb ceramic carrier comprise: sintering aid: 10%, titanium nitride: 10%, dispersion agent: 2%, rare earth oxide: 4%, carbon fiber: 2%, all the other are alumina powder jointed.Wherein MgO, SiO of sintering aid to be mass ratio be 2:1:1
2and Fe
2o
3dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide; Wherein silicon carbide fiber is (this place pretreating scheme can also be applicable to include, without being limited to the present invention and enumerate other embodiment in interior all technical schemes) through argon plasma surface preparation.Wherein the open porosity of ceramic honey comb is 70%, and straight way is 2:1 with the pore volume ratio of serpentine channel.
Embodiment 3
The vehicle tail gas purification device of the present embodiment, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is arranged in housing, and the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of honeycomb ceramic carrier comprise: sintering aid: 15%, titanium nitride: 6%, dispersion agent: 5%, rare earth oxide: 2%, carbon fiber: 1.5%, all the other are alumina powder jointed.Wherein CaO, V of sintering aid to be mass ratio be 2:2:1:1
2o
5, Fe
2o
3and TiO
2dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide.Wherein the open porosity of ceramic honey comb is 72%, and straight way is 8:5 with the pore volume ratio of serpentine channel.
Embodiment 4
The vehicle tail gas purification device of the present embodiment, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is arranged in housing, and the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of honeycomb ceramic carrier comprise: sintering aid: 11%, titanium nitride: 5%, dispersion agent: 5%, rare earth oxide: 3%, silicon carbide fiber: 1%, all the other are alumina powder jointed.Wherein MgO, CaO, V of sintering aid to be mass ratio be 3:1:1:1
2o
5and TiO
2dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide.Wherein the open porosity of ceramic honey comb is 80%, and straight way is 7:4 with the pore volume ratio of serpentine channel.
Embodiment 5
The vehicle tail gas purification device of the present embodiment, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is arranged in housing, and the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of honeycomb ceramic carrier comprise: sintering aid: 13%, titanium nitride: 8%, dispersion agent: 3%, rare earth oxide: 5%, carbon fiber: 1.5%, all the other are alumina powder jointed.Wherein MgO, CaO, SiO of sintering aid to be mass ratio be 1:1:1:1:1:1
2, V
2o
5, Fe
2o
3and TiO
2dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide.Wherein the open porosity of ceramic honey comb is 76%, and straight way is 7:5 with the pore volume ratio of serpentine channel.
The difference of embodiment 6-10 and embodiment 1-5 be only described alumina powder jointed particle diameter be respectively 200,160,175,180,150nm.
The difference of embodiment 11-15 and embodiment 6-10 is only that described dispersion agent mesosilicic acid sodium, glycerine, carboxymethyl cellulose, stearic mass ratio are respectively 3:7:1:1,5:7:3:1,4:9:2:1,4:8:2:1,3:9:2:1.
Embodiment 16
The preparation method of the present embodiment vehicle tail gas purification device, step is as follows:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, mixed powder is fully mixed with the mass ratio of 80:100 with water, add dispersion agent and silicon carbide fiber again, be uniformly dispersed and obtain ceramic size;
Wherein alumina powder jointed, sintering aid, titanium nitride, rare earth oxide, dispersion agent and silicon carbide fiber mass ratio is 78:10:4:4:3:1, wherein MgO and CaO of sintering aid to be mass ratio be 1:1, dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide;
2) slurry is passed through the shaping base of extrusion shaping machine, obtain biscuit;
3) sinter: a. is by biscuit at ambient pressure after 1100 DEG C of sintering 60min, and b. regulates pressure to 20MPa, adjust the temperature to 900 DEG C of continuation sintering 30min, c. and at 700 DEG C, be incubated 90min again, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again; Wherein apply to be divided into and complete for twice, second time coating wet weightening finish ratio first time weighs 55%, and the carrier percentage of plugged hole after coating is less than 1%.
5) subsequent disposal: by step 4) assemble with housing after the carrier drying that obtains and calcination process, make vehicle tail gas purification device.
Embodiment 17
The preparation method of the present embodiment vehicle tail gas purification device, step is as follows:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, mixed powder is fully mixed with the mass ratio of 81:100 with water, add dispersion agent and carbon fiber again, be uniformly dispersed and obtain ceramic size;
Wherein alumina powder jointed, sintering aid, titanium nitride, rare earth oxide, dispersion agent and carbon fiber mass ratio is 72:14:6:5:2:1, wherein MgO and Fe of sintering aid to be mass ratio be 1:1
2o
3dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide;
2) slurry is passed through the shaping base of extrusion shaping machine, obtain biscuit;
3) sinter: a. is by biscuit at ambient pressure after 1100 DEG C of sintering 65min, and b. regulates pressure to 20MPa, adjust the temperature to 1100 DEG C of continuation sintering 40min, c. and at 650 DEG C, be incubated 100min again, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again; Wherein apply to be divided into and complete for twice, second time coating wet weightening finish ratio first time weighs 52%, and the carrier percentage of plugged hole after coating is less than 1%.
5) subsequent disposal: by step 4) assemble with housing after the carrier drying that obtains and calcination process, make vehicle tail gas purification device.
Embodiment 18
The preparation method of the present embodiment vehicle tail gas purification device, step is as follows:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, mixed powder is fully mixed with the mass ratio of 83:100 with water, add dispersion agent and silicon carbide fiber again, be uniformly dispersed and obtain ceramic size;
Wherein alumina powder jointed, sintering aid, titanium nitride, rare earth oxide, dispersion agent and silicon carbide fiber mass ratio is 68:15:7:5:3:2, wherein CaO, V of sintering aid to be mass ratio be 2:2:1
2o
5and Fe
2o
3dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide;
2) slurry is passed through the shaping base of extrusion shaping machine, obtain biscuit;
3) sinter: a. is by biscuit at ambient pressure after 1200 DEG C of sintering 75min, and b. regulates pressure to 20MPa, adjust the temperature to 1000 DEG C of continuation sintering 45min, c. and at 600 DEG C, be incubated 110min again, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again; Wherein apply to be divided into and complete for twice, second time coating wet weightening finish ratio first time weighs 49%, and the carrier percentage of plugged hole after coating is less than 1%.
5) subsequent disposal: by step 4) assemble with housing after the carrier drying that obtains and calcination process, make vehicle tail gas purification device.
Embodiment 19
The preparation method of the present embodiment vehicle tail gas purification device, step is as follows:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, mixed powder is fully mixed with the mass ratio of 84:100 with water, add dispersion agent and carbon fiber again, be uniformly dispersed and obtain ceramic size;
Wherein alumina powder jointed, sintering aid, titanium nitride, rare earth oxide, dispersion agent and carbon fiber mass ratio is 71:10:10:2:5:2, wherein MgO, V of sintering aid to be mass ratio be 3:1:1
2o
5and TiO
2dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide;
2) slurry is passed through the shaping base of extrusion shaping machine, obtain biscuit;
3) sinter: a. is by biscuit at ambient pressure after 1150 DEG C of sintering 80min, and b. regulates pressure to 20MPa, adjust the temperature to 1000 DEG C of continuation sintering 55min, c. and at 550 DEG C, be incubated 110min again, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again; Wherein apply to be divided into and complete for twice, second time coating wet weightening finish ratio first time weighs 46%, and the carrier percentage of plugged hole after coating is less than 1%.
5) subsequent disposal: by step 4) assemble with housing after the carrier drying that obtains and calcination process, make vehicle tail gas purification device.
Embodiment 20
The preparation method of the present embodiment vehicle tail gas purification device, step is as follows:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, mixed powder is fully mixed with the mass ratio of 85:100 with water, add dispersion agent and carbon fiber again, be uniformly dispersed and obtain ceramic size;
Wherein alumina powder jointed, sintering aid, titanium nitride, rare earth oxide, dispersion agent and carbon fiber mass ratio is 70:11:9:5:4:1, wherein MgO and TiO of sintering aid to be mass ratio be 1:1
2dispersion agent is water glass, glycerine, carboxymethyl cellulose, stearic mixture, and rare earth oxide can be one or both and two or more mixtures in the rare earth oxides such as lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, dysprosium oxide, promethium oxide;
2) slurry is passed through the shaping base of extrusion shaping machine, obtain biscuit;
3) sinter: a. is by biscuit at ambient pressure after 1150 DEG C of sintering 90min, and b. regulates pressure to 20MPa, adjust the temperature to 1050 DEG C of continuation sintering 60min, c. and at 500 DEG C, be incubated 120min again, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again; Wherein apply to be divided into and complete for twice, second time coating wet weightening finish ratio first time weighs 45%, and the carrier percentage of plugged hole after coating is less than 1%.
5) subsequent disposal: by step 4) assemble with housing after the carrier drying that obtains and calcination process, (calcination process technique carries out adding thermal bake-out for dried carrier being put into stoving oven by following temperature curve to make vehicle tail gas purification device, time controling is at 5h: one district: 170-190 DEG C, 2nd district: 200-240 DEG C, 3rd district: 280-320 DEG C, 4th district: 370-500 DEG C, 5th district: 500-520 DEG C.Roasting time can also be 5.1,5.1,5.3,5.5,5.7,5.9,6,7, other random times between 8h and 5-8h.This place pretreating scheme can also be applicable to include, without being limited to the present invention and enumerate other embodiment in interior all technical schemes).
The honeycomb ceramic carrier getting each embodiment measures thermal conductivity, and measures its thermal expansivity and ultimate compression strength according to GB/T25994-2010, and wherein the test data of embodiment 5,10,15,20 lists in table 1.
Comparative example
Take mass ratio as alumina powder jointed, the SiO of 49:33:13
2be that raw material makes honeycomb ceramic carrier according to common method for making with MgO, then measure its thermal conductivity, and measure its thermal expansivity, ultimate compression strength according to GB/T25994-2010, the data obtained lists in table 1.
Table 1
After measured, thermal expansivity is all not more than 2.00 × 10 to each embodiment gained honeycomb ceramic carrier above
-6dEG C
-1, ultimate compression strength A direction of principal axis is all not less than 15.0MPa, and B direction of principal axis is all not less than 4.5MPa, and C direction of principal axis is all not less than 0.7MPa, and thermal conductivity is all not less than 20 (W/ (mK)).
In view of the present invention program's embodiment is numerous, each embodiment experimental data is huge numerous, be not suitable for particularize herein to illustrate, but the content of the required checking of each embodiment is all close with the final conclusion obtained, so do not illustrate one by one the checking content of each embodiment herein.
The technical scope mid point value non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technique means disclosed in the present invention program is not limited only to the technique means disclosed in above-mentioned technique means, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a vehicle tail gas purification device, comprise housing and honeycomb ceramic carrier, honeycomb ceramic carrier is arranged in housing, it is characterized in that: the vesicular structure of described honeycomb ceramic carrier comprises bending serpentine channel and straight way, and straight way is communicated on serpentine channel, component and the massfraction thereof of described honeycomb ceramic carrier comprise: sintering aid: 10-15%, titanium nitride: 4-10%, dispersion agent: 2-5%, rare earth oxide: 2-5%, fortifying fibre: 1-2%, surplus is alumina powder jointed.
2. vehicle tail gas purification device according to claim 1, is characterized in that: the open porosity of described honeycomb ceramic carrier is 70-80%.
3. vehicle tail gas purification device according to claim 1, is characterized in that: the pore volume of described straight way and serpentine channel is than being (7-8): (4-5).
4. vehicle tail gas purification device according to claim 1, is characterized in that: described alumina powder jointed particle diameter is 150-200nm.
5. vehicle tail gas purification device according to claim 1, is characterized in that: described sintering aid is MgO, CaO, SiO
2, V
2o
5, Fe
2o
3, TiO
2in at least two kinds.
6. vehicle tail gas purification device according to claim 1, is characterized in that: the mass ratio of described titanium nitride and rare earth oxide is (3-5): 2.
7. vehicle tail gas purification device according to claim 1, is characterized in that: described dispersion agent comprises water glass, glycerine, carboxymethyl cellulose, stearic acid.
8. vehicle tail gas purification device according to claim 7, is characterized in that: described dispersion agent mesosilicic acid sodium, glycerine, carboxymethyl cellulose, stearic mass ratio are (3-5): (7-9): (1-3): 1.
9. vehicle tail gas purification device according to claim 1, is characterized in that: described fortifying fibre is the one in silicon carbide fiber or carbon fiber.
10. a preparation method for vehicle tail gas purification device, is characterized in that comprising the steps:
1) ceramic size preparation: alumina powder jointed, sintering aid, titanium nitride, rare earth oxide are mixed and obtain mixed powder, by mixed powder with water with (80-85): the mass ratio of 100 fully mixes, add dispersion agent and fortifying fibre again, be uniformly dispersed and obtain ceramic size;
2) shaping base, obtains biscuit;
3) sinter: after biscuit is sintered 60-90min in 1100-1200 DEG C by a. at ambient pressure, b. regulate pressure to 20MPa, adjust the temperature to 900-1100 DEG C of continuation sintering 30-60min, c. and at 500-700 DEG C, be incubated 90-120min again, obtain honeycomb ceramic carrier;
4) carrier coating and dipping: pulp solution is coated on obtained honeycomb ceramic carrier surface, after drying process, the active component solution put into by carrier containing palladium, platinum, rhodium carries out dip treating again;
5) subsequent disposal: by step 4) assemble with housing after the carrier drying that obtains and calcination process, make vehicle tail gas purification device.
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| CN107032818A (en) * | 2017-02-28 | 2017-08-11 | 韦尧天 | A kind of heat-insulation and heat-preservation ceramics and preparation method thereof |
| CN107840636A (en) * | 2017-09-18 | 2018-03-27 | 深圳市奥工电子科技有限公司 | Purifying vehicle exhaust energy ceramics and preparation method thereof |
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| CN104072111A (en) * | 2013-03-29 | 2014-10-01 | 北京市理化分析测试中心 | Preparation method of aluminium oxide honeycomb ceramics |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107032818A (en) * | 2017-02-28 | 2017-08-11 | 韦尧天 | A kind of heat-insulation and heat-preservation ceramics and preparation method thereof |
| CN107840636A (en) * | 2017-09-18 | 2018-03-27 | 深圳市奥工电子科技有限公司 | Purifying vehicle exhaust energy ceramics and preparation method thereof |
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