Patent Application
20140112835
The present invention relates to a honeycomb structure, a method for manufacturing the honeycomb structure, an exhaust gas purifying apparatus and silicoaluminophosphate particles.
In the related art, a selective catalytic reduction (SCR) system that reduces NOx into nitrogen and water using ammonia is known as one of many systems that purify exhaust gas from vehicles.
In addition, zeolite is known as a material that adsorbs ammonia in the selective catalytic reduction system.
PTL 1 discloses a honeycomb structure including a honeycomb unit that contains zeolite, an inorganic fiber and/or whisker, and an inorganic binder.
Meanwhile, SAPO-34 is known as zeolite having excellent NOx purification performance.
[PTL 1] PCT International Publication No. WO 06/137149
However, SAPO-34 contracts or expands due to the adsorption or desorption of water, which causes a change in the lattice constant. Therefore, in the honeycomb structure including honeycomb unit that contains SAPO-34, there is a problem in that the honeycomb unit is easily broken due to SAPO-34 adsorbing or desorbing water.
The invention has been made in consideration of the problem of the related art, and an object of the invention is to provide a honeycomb structure that has excellent NOx purification performance and can suppress the breakage of a honeycomb unit due to the adsorption or desorption of water, a method for manufacturing the honeycomb structure, and an exhaust gas purifying apparatus including the honeycomb structure.
In addition, another object of the invention is to provide silicoaluminophosphate particles that has excellent NOx purification performance and can suppress water adsorption-caused contraction and water desorption-caused expansion.
A honeycomb structure of the invention includes a honeycomb unit provided with a plurality of through holes arrayed in a longitudinal direction with a partition wall therebetween, in which the honeycomb unit is produced by extruding and firing raw material paste containing silicoaluminophosphate particles and an inorganic binder, and the silicoaluminophosphate particles have a specific surface area in a range of 200 m2/g to 400 m2/g and an acid point of 1.2 mmol/g or more.
The acid point of the silicoaluminophosphate particles is desirably equal to or smaller than a value computed using a formula
(Ratio of an amount of Si to a sum of amounts of Al and P)×12.9 [mmol/g].
The silicoaluminophosphate particles are desirably ion-exchanged with copper ions and/or iron ions.
In the honeycomb unit, a content of the silicoaluminophosphate particles per apparent volume is desirably in a range of 230 g/L to 360 g/L. Meanwhile, the apparent volume refers to a volume of an outer circumference including a volume of voids.
The inorganic binder is desirably a solid content contained in one or more selected from a group consisting of an alumina sol, a silica sol, a titania sol, water glass, sepiolite, attapulgite and boehmite.
The raw material paste desirably further contains one or more selected from a group consisting of inorganic fibers, scale-like substances, tetrapot-like substances and three dimensional needle-like substances.
The inorganic fiber is desirably one or more selected from a group consisting of alumina, silica, silicon carbide, silica alumina, glass, potassium titanate and aluminum borate; the scale-like substance is desirably one or more selected from a group consisting of glass, muscovite, alumina and silica; the tetrapot-like substance is desirably zinc oxide; and the three dimensional needle-like substance is desirably one or more selected from a group consisting of alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate and boehmite.
The honeycomb structure of the invention desirably includes a plurality of the honeycomb units.
In the honeycomb structure of the invention, an NOx purification rate is desirably 85% or more in a case in which 200° C.-hot simulant gas is made to flow into the honeycomb structure so that a space velocity becomes 80000/h, the space velocity is desirably a ratio of a flow rate [m3/h] of the simulant gas to an apparent volume [m3] of the honeycomb structure, and the simulant gas desirably contains nitrogen monoxide at a concentration of 350 ppm, ammonia at a concentration of 350 ppm, oxygen at a concentration of 10%, water at a concentration of 5% and carbon dioxide at a concentration of 5% with a balance of nitrogen.
A method for manufacturing the honeycomb structure of the invention is a method for manufacturing the honeycomb structure including a honeycomb unit provided with a plurality of through holes arrayed in a longitudinal direction with a partition wall therebetween, including a step of extruding raw material paste containing silicoaluminophosphate particles and an inorganic binder; and a step of firing the extruded raw material paste so as to produce the honeycomb unit, in which the silicoaluminophosphate particles have a specific surface area in a range of 200 m2/g to 400 m2/g, and an acid point of 1.2 mmol/g or more.
The acid point of the silicoaluminophosphate particles is desirably equal to or smaller than a value computed using a formula
(Ratio of an amount of Si to a sum of amounts of Al and P)×12.9 [mmol/g].
An exhaust gas purifying apparatus of the invention is accommodated in a metal container in a state in which a holding seal material is disposed on an outer circumferential surface of the honeycomb structure of the invention excluding both end surfaces.
The silicoaluminophosphate particles of the invention have a specific surface area in a range of 200 m2/g to 400 m2/g and an acid point of 1.2 mmol/g or more.
The acid point of the silicoaluminophosphate particles is desirably equal to or smaller than a value computed using a formula
(Ratio of an amount of Si to a sum of amounts of Al and P)×12.9 [mmol/g].
According to the invention, it is possible to provide a honeycomb structure that has excellent NOx purification performance and can suppress the breakage of a honeycomb unit due to the adsorption or desorption of water, a method for manufacturing the honeycomb structure, and an exhaust gas purifying apparatus including the honeycomb structure.
In addition, according to the invention, it is possible to provide silicoaluminophosphate particles that has excellent NOx purification performance and can suppress water adsorption-caused contraction and water desorption-caused expansion.
Next, embodiments for carrying out the invention will be described with reference to the accompanying drawings.
Hereinafter, the silicoaluminophosphate particles refer to the silicoaluminophosphate particles contained in the raw material paste.
The specific surface area of the silicoaluminophosphate particles is in a range of 200 m2/g to 400 m2/g, preferably in a range of 220 m2/g to 380 m2/g, more preferably in a range of 250 m2/g to 360 m2/g, and still more preferably in a range of 280 m2/g to 330 m2/g. When the specific surface area of the silicoaluminophosphate particles is less than 200 m2/g, since the number of pores in the honeycomb unit 11 decreases, exhaust gas cannot easily infiltrate into an inside of the partition wall 11b in the honeycomb unit 11, and it becomes impossible to effectively use the silicoaluminophosphate particles for NOx purification. On the other hand, when the specific surface area of the silicoaluminophosphate particles exceeds 400 m2/g, it becomes difficult to suppress the water adsorption-caused contraction and water desorption-caused expansion of the silicoaluminophosphate particles.
Generally, the specific surface area of the silicoaluminophosphate particles is approximately 500 m2/g; however, in the invention, it is possible to set the specific surface area of the silicoaluminophosphate particles to 400 m2/g or less by carrying out an alkali treatment on the silicoaluminophosphate particles so as to make some crystals amorphous.
An alkali used in the alkali treatment is not particularly limited, and examples thereof include ammonia, sodium hydroxide and the like.
Meanwhile, the specific surface area of the silicoaluminophosphate particles can be measured using a BET multipoint method (N2 adsorption method). In addition, when the specific surface area of the silicoaluminophosphate particles is measured, for example, an automatic surface area and porosimetry analyzer TriStar-3000 (manufactured by Shimadzu Corporation) can be used.
The acid point of the silicoaluminophosphate particles is 1.2 mmol/g or more, preferably 1.5 mmol/g or more, and more preferably 2.2 mmol/g or more. If the acid point of the silicoaluminophosphate particles is less than 1.2 mmol/g, when the silicoaluminophosphate particles are ion-exchanged, the ion exchange amount decreases, and an effect that improves NOx purification performance becomes small. At this time, the acid point of the silicoaluminophosphate particles is equal to or smaller than a theoretical value computed using a formula
(Ratio of an amount of Si to a sum of amounts of Al and P)×12.9 [mmol/g],
and is preferably 1.32 mmol/g to 2.32 mmol/g.
Meanwhile, the acid point of the silicoaluminophosphate particles can be measured using an ammonia thermal desorption method.
The silicoaluminophosphate particles preferably have a specific surface area in a range of 220 m2/g to 380 m2/g and an acid point of 1.32 mmol/g to 2.32 mmol/g. Then, the honeycomb structure 10 that has superior NOx purification performance and can further suppress the breakage of the honeycomb unit due to the adsorption or desorption of water can be obtained.
In the silicoaluminophosphate particles, the ratio of the amount of Si to the sum of the amounts of Al and P is preferably in a range of 0.16 to 0.33. When the ratio of the amount of Si to the sum of the amounts of Al and P in the silicoaluminophosphate particles is less than 0.16, it becomes difficult to suppress the water adsorption-caused contraction and water desorption-caused expansion of the silicoaluminophosphate particles. On the other hand, when the ratio of the amount of Si to the sum of the amounts of Al and P in the silicoaluminophosphate particles exceeds 0.33, the silicoaluminophosphate particles become amorphous, and it becomes difficult to produce the honeycomb unit 11.
Meanwhile, as the unit of the amount in the invention, ‘mol’ is used, and the ratio (molar ratio) of the amount [mol] of Si to the sum of the amounts [mol] of Al and P in the silicoaluminophosphate particles can be measured using energy dispersive X-ray spectroscopy (EDS).
The silicoaluminophosphate particles can be produced by adding phosphoric acid, aluminum hydroxide, silica and a structure directing agent (SDA) to water so as to produce a precursor gel, and then carrying out heating and an alkali treatment on the precursor gel.
Meanwhile, the structure directing agent refers to a mold used to form a fine regular structure when producing the silicoaluminophosphate particles.
At this time, it is possible to control the acid point of the silicoaluminophosphate particles by adjusting the addition amount of the structure directing agent. In addition, it is possible to control the ratio of the amount of Si to the sum of the amounts of Al and P in the silicoaluminophosphate particles by adjusting the ratio of the amount of silica to the sum of the amounts of the phosphoric acid and the aluminum hydroxide. Also, it is possible to control the specific surface area of the silicoaluminophosphate particles by adjusting the condition of the alkali treatment.
The structure directing agent is not particularly limited, examples thereof include morpholine, diethylamine, tetraethylammonium hydroxide, triethylamine and the like, and two or more structure directing agents may be jointly used.
The silicoaluminophosphate particles are preferably ion-exchanged with copper ions and/or iron ions in consideration of NOx purification performance.
In the silicoaluminophosphate particles being ion-exchanged with copper ions and/or iron ions, the ion exchange amount is preferably in a range of 1.0% by mass to 5.0% by mass. When the ion exchange amount of the silicoaluminophosphate particles is less than 1.0% by mass, the effect that improves NOx purification performance becomes small. On the other hand, when the ion exchange amount of the silicoaluminophosphate particles exceeds 5.0% by mass, hydrothermal durability degrades, and NOx purification performance degrades at a high temperature of, for example, 500° C. or higher.
Meanwhile, the silicoaluminophosphate particles may be ion-exchanged with other metallic ions.
The average diameter of original silicoaluminophosphate particles of the silicoaluminophosphate particles is preferably in a range of 2.0 μm to 6.0 μm. When the average diameter of original silicoaluminophosphate particles of the silicoaluminophosphate particles is less than 2.0 μm, exhaust gas cannot easily infiltrate into the inside of the partition wall 11b, and it becomes impossible to effectively use the silicoaluminophosphate particles for NOx purification. On the other hand, when the average diameter of original silicoaluminophosphate particles of the silicoaluminophosphate particles exceeds 6.0 μm, the porosity of the honeycomb unit 11 increases such that the strength of the honeycomb unit 11 decreases or the specific surface area of the silicoaluminophosphate particles decreases such that NOx purification performance degrades.
Generally, the average diameter of original silicoaluminophosphate particles of the silicoaluminophosphate particles is approximately 20 μm, but the average diameter of original silicoaluminophosphate particles can be decreased by crushing the silicoaluminophosphate particles.
Meanwhile, the average diameter of original silicoaluminophosphate particles of the silicoaluminophosphate particles can be measured using a laser diffraction-type particle size distribution analyzer.
In the honeycomb unit 11, the content of the silicoaluminophosphate particles per apparent volume is preferably in a range of 230 g/L to 360 g/L. When the content of the silicoaluminophosphate particles per apparent volume of the honeycomb unit 11 is less than 230 g/L, it is necessary to increase the apparent volume of the honeycomb unit 11 in order to improve NOx purification performance. On the other hand, when the content of the silicoaluminophosphate particles per apparent volume of the honeycomb unit 11 exceeds 360 g/L, the strength of the honeycomb unit 11 becomes insufficient, or the aperture ratio of the honeycomb unit 11 becomes small.
Meanwhile, the apparent volume refers to the volume of the outer circumference including the volume of voids.
The inorganic binder contained in the raw material paste is not particularly limited, examples thereof include solid contents contained in an alumina sol, a silica sol, a titania sol, water glass, sepiolite, attapulgite, boehmite and the like, and two or more inorganic binders may be jointly used.
The content of the inorganic binder contained in the solid content of the raw material paste is preferably in a range of 5% by mass to 30% by mass, and more preferably in a range of 10% by mass to 20% by mass. When the content of the inorganic binder in the solid content of the raw material paste is less than 5% by mass, the strength of the honeycomb unit 11 decreases. On the other hand, when the content of the solid content of the inorganic binder contained in the solid content of the raw material paste exceeds 30% by mass, it becomes difficult to extrude the honeycomb unit 11.
The raw material paste preferably further contains one or more selected from a group consisting of inorganic fibers, scale-like substances, tetrapot-like substances and three dimensional needle-like substances in order to improve the strength of the honeycomb unit 11.
A material that configures the inorganic fiber contained in the raw material paste is not particularly limited, examples thereof include alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate and the like, and two or more materials may be jointly used.
The aspect ratio of the inorganic fiber contained in the raw material paste is preferably in a range of 2 to 1000, more preferably in a range of 5 to 800, and still more preferably in a range of 10 to 500. When the aspect ratio of the inorganic fiber contained in the raw material paste is smaller than 2, the effect that improves the strength of the honeycomb unit 11 becomes small. On the other hand, when the aspect ratio of the inorganic fiber contained in the raw material paste exceeds 1000, clogging and the like occur in a mold when extruding the honeycomb unit 11 or the inorganic fiber breaks such that the effect that improves the strength of the honeycomb unit 11 becomes small.
The scale-like substance refers to a flat substance, the thickness is preferably in a range of 0.2 μm to 5.0 μm, the maximum length is preferably in a range of 10 μm to 160 μm, and the ratio of the maximum length to the thickness is preferably in a range of 3 to 250.
A material that configures the scale-like substance contained in the raw material paste is not particularly limited, examples thereof include glass, muscovite, alumina, silica and the like, and two or more materials may be jointly used.
The tetrapot-like substance refers to a substance in which a needle-like portion three-dimensionally extends, the average length of the needle shapes in the needle-like portion is preferably in a range of 5 μm to 30 μm, and the average diameter of the needle-like portion is preferably in a range of 0.5 μm to 5.0 μm.
A material that configures the tetrapot-like substance contained in the raw material paste is not particularly limited, examples thereof include zinc oxide, and two or more materials may be jointly used.
The three dimensional needle-like substance refers to a substance in which needle-like portions are bonded to each other near the centers of the respective needle-like portions through an inorganic compound such as glass, the average length of the needle shapes in the needle-like portion is preferably in a range of 5 μm to 30 μm, and the average diameter of the needle-like portion is preferably in a range of 0.5 μm to 5.0 μm.
In addition, in the three dimensional needle-like substance, a plurality of needle-like portions may be connected to each other three-dimensionally, the diameter of the needle-like portion is preferably in a range of 0.1 μm to 5.0 μm, the length is preferably in a range of 0.3 μm to 30.0 μm, and the ratio of the length to the diameter is preferably in a range of 1.4 to 50.0.
A material that configures the three dimensional needle-like substance contained in the raw material paste is not particularly limited, examples thereof include alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate, boehmite and the like, and two or more materials may be jointly used.
The content of the inorganic fibers, the scale-like substances, the tetrapot-like substances and the three dimensional needle-like substances in the solid content of the raw material paste is preferably in a range of 3% by mass to 50% by mass, more preferably in a range of 3% by mass to 30% by mass, and still more preferably in a range of 5% by mass to 20% by mass. When the content of the inorganic fibers, the scale-like substances, the tetrapot-like substances and the three dimensional needle-like substances in the solid content of the raw material paste is less than 3% by mass, the effect that improves the strength of the honeycomb unit 11 becomes small. On the other hand, when the content of the inorganic fibers, the scale-like substances, the tetrapot-like substances and the three dimensional needle-like substances in the solid content of the raw material paste exceeds 50% by mass, the content of the silicoaluminophosphate particles in the honeycomb unit 11 decreases, and NOx purification performance degrades.
The porosity of the honeycomb unit 11 is preferably in a range of 40% to 60%. When the porosity of the honeycomb unit 11 is less than 40%, exhaust gas cannot easily infiltrate into the inside of the partition wall 11b, and it becomes impossible to effectively use the silicoaluminophosphate particles for NOx purification. On the other hand, when the porosity of the honeycomb unit 11 exceeds 60%, the strength of the honeycomb unit 11 comes insufficient.
Meanwhile, the porosity of the honeycomb unit 11 can be measured using a mercury intrusion method.
The aperture ratio of the honeycomb unit 11 in a cross-section vertical to the longitudinal direction is preferably in a range of 50% to 75%. When the aperture ratio of the honeycomb unit 11 in a cross-section vertical to the longitudinal direction is less than 50%, it becomes impossible to effectively use the silicoaluminophosphate particles for NOx purification. On the other hand, when the aperture ratio of the honeycomb unit 11 in a cross-section vertical to the longitudinal direction exceeds 75%, the strength of the honeycomb unit 11 becomes insufficient.
The density of the through holes 11a in the honeycomb unit 11 on a cross-section vertical to the longitudinal direction is preferably in a range of 31 holes/cm2 to 155 holes/cm2. When the density of the through holes 11a in the honeycomb unit 11 on a cross-section vertical to the longitudinal direction is less than 31 holes/cm2, it becomes difficult for the silicoaluminophosphate particles to come into contact with exhaust gas, and NOx purification performance degrades. On the other hand, when the density of the through holes 11a in the honeycomb unit 11 on a cross-section vertical to the longitudinal direction exceeds 155 holes/cm2, the pressure loss of the honeycomb structure 10 increases.
The thickness of the partition wall 11b in the honeycomb unit 11 is preferably in a range of 0.10 mm to 0.50 mm, and more preferably in a range of 0.15 mm to 0.35 mm. When the thickness of the partition wall 11b is less than 0.10 mm, the strength of the honeycomb unit 11 decreases. On the other hand, when the thickness of the partition wall 11b exceeds 0.50 mm, exhaust gas cannot easily infiltrate into the inside of the partition wall 11b, and it becomes impossible to effectively use the silicoaluminophosphate particles for NOx purification.
The thickness of the outer circumference coating layer 12 is preferably in a range of 0.1 mm to 2.0 mm. When the thickness of the outer circumference coating layer 12 is less than 0.1 mm, the effect that improves the strength of the honeycomb structure 10 becomes insufficient. On the other hand, when the thickness of the outer circumference coating layer 12 exceeds 2.0 mm, the content of the silicoaluminophosphate particles per unit volume of the honeycomb structure 10 decreases such that NOx purification performance degrades.
The shape of the honeycomb structure 10 is not limited to a circular column shape, and examples thereof include a column shape, an oval column shape, a long circular column shape, a round-chamferred rectangular column shape (for example, a round-chamferred triangular column shape) and the like.
The shape of the through hole 11a is not limited to a rectangular column shape, and examples thereof include a triangular column shape, a hexagonal column shape and the like.
In the honeycomb structure 10, the NOx purification rate is preferably 85% or more in a case in which 200° C.-hot simulant gas is made to flow so that the space velocity becomes 80000/h. At this time, the space velocity refers to the ratio of the flow rate [m3/h] of the simulant gas to the apparent volume [m3] of the honeycomb structure 10, and the simulant gas contains nitrogen monoxide at a concentration of 350 ppm, ammonia at a concentration of 350 ppm, oxygen at a concentration of 10%, water at a concentration of 5% and carbon dioxide at a concentration of 5% with a balance of nitrogen.
Next, an example of the method for manufacturing the honeycomb structure 10 will be described. First, raw material paste containing the silicoaluminophosphate particles and the inorganic binder, and, furthermore, one or more selected from a group consisting of inorganic fibers, scale-like substances, tetrapot-like substances and three dimensional needle-like substances as necessary is extruded, thereby producing a circular column-shaped honeycomb compact provided with a plurality of through holes arrayed in the longitudinal direction with a partition wall therebetween.
At this time, the raw material paste may further contain an organic binder, a dispersion medium, a molding assistant and the like as necessary.
The organic binder is not particularly limited, examples thereof include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, phenol resins, epoxy resins and the like, and two or more organic binders may be jointly used.
The content of the organic binder in the raw material paste is preferably in a range of 1% by mass to 10% by mass with respect to the total amount of the silicoaluminophosphate particles, the inorganic binder, the inorganic fiber, the scale-like substance, the tetrapot-like substance and the three dimensional needle-like substance.
The dispersion medium is not particularly limited, examples thereof include water, organic solvents such as benzene, alcohols such as methanol, and the like, and two or more dispersion media may be jointly used.
The molding assistant is not particularly limited, examples thereof include ethylene glycol, dextrin, aliphatic acids, aliphatic soap, polyalcohols and the like, and two or more molding assistants may be jointly used.
When preparing the raw material paste, the components are preferably mixed and kneaded. The components may be mixed using a mixer, an attritor or the like, and may be kneaded using a kneader or the like.
Next, the honeycomb compact is dried using a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a reduced-pressure dryer, a vacuum dryer or a freeze dryer, thereby producing a dried honeycomb.
Furthermore, the dried honeycomb is defatted, thereby producing a defatted honeycomb. The defatting conditions can be appropriately selected depending on the kinds and amounts of organic substances contained in the dried honeycomb, and the dried honeycomb is preferably defatted at 400° C. for 2 hours.
Next, the defatted honeycomb is fired, thereby producing a circular column-shaped honeycomb unit 11. The firing temperature is preferably in a range of 600° C. to 1200° C., and more preferably in a range of 600° C. to 1000° C. When the firing temperature is lower than 600° C., sintering does not proceed, and the strength of the honeycomb unit 11 decreases. On the other hand, when the firing temperature exceeds 1200° C., sintering excessively proceeds such that the number of reaction sites of the silicoaluminophosphate particles decreases.
Next, paste for outer circumference coating layers is applied to the outer circumferential surface of the circular column-shaped honeycomb unit 11 excluding both end surfaces.
The paste for outer circumference coating layers is not particularly limited, and examples thereof include mixtures of an inorganic binder and inorganic particles, mixtures of an inorganic binder and an inorganic fiber, mixtures of an inorganic binder, inorganic particles and an inorganic fiber, and the like.
The inorganic binder contained in the paste for outer circumference coating layers is not particularly limited, examples thereof include solid content contained in a silica sol, an alumina sol or the like, and two or more inorganic binders may be jointly used. Among the above, the solid content contained in silica sol is preferable.
A material that configures the inorganic particles contained in the paste for outer circumference coating layers is not particularly limited, examples thereof include carbides such as silicon carbide, nitrides such as silicon nitride and boron nitride, and the like, and two or more inorganic particles may be jointly used. Among the above, silicon carbide is preferable due to the excellent thermal conductivity.
A material that configures the inorganic fiber contained in the paste for outer circumference coating layers is not particularly limited, examples thereof include silica alumina, mullite, alumina, silica and the like, and two or more inorganic fibers may be jointly used. Among the above, alumina is preferable.
The paste for outer circumference coating layers may further contain an organic binder.
The organic binder contained in the paste for outer circumference coating layers is not particularly limited, examples thereof include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and the like, and two or more organic binders may be jointly used.
The paste for outer circumference coating layers may further contain a balloon that is a minute hollow sphere of an oxide-based ceramic, a pore-forming agent and the like.
The balloon contained in the paste for outer circumference coating layers is not particularly limited, examples thereof include alumina balloons, glass micro balloons, shirasu balloons, fly ash balloons, mullite balloons and the like, and two or more balloons may be jointly used. Among the above, alumina balloons are preferable.
The pore-forming agent contained in the paste for outer circumference coating layers is not particularly limited, examples thereof include spherical acrylic particles, graphite and the like, and two or more pore-forming agents may be jointly used.
Next, the honeycomb unit 11 to which the paste for outer circumference coating layers has been applied is dried and solidified, thereby producing a circular column-shaped honeycomb structure 10. At this time, in a case in which the paste for outer circumference coating layers contains the organic binder, the paste for outer circumference coating layers is preferably defatted. The defatting conditions can be appropriately selected depending on the kinds and amounts of organic substances, and the paste for outer circumference coating layers is preferably defatted at 600° C. for 1 hour.
Meanwhile, the silicoaluminophosphate particles can be ion-exchanged by immersing the honeycomb unit 11 in an aqueous solution containing copper ions and/or iron ions.
In addition, raw material paste containing silicoaluminophosphate particles which have been ion-exchanged with copper ions and/or iron ions may also be used.
The compound that generates ammonia when being decomposed is not particularly limited as long as the compound is heated by exhaust gas in the pipe so as to generate ammonia, but aqueous urea is preferable due to the excellent storage stability.
The aqueous urea is heated by exhaust gas in the pipe and hydrolyzed, thereby generating ammonia.
The cross-sectional area of a cross-section of the honeycomb unit 11′ vertical to the longitudinal direction is preferably in a range of 5 cm2 to 50 cm2. When the cross-sectional area of a cross-section of the honeycomb unit 11′ vertical to the longitudinal direction is smaller than 5 cm2, the pressure loss of the honeycomb structure 10′ increases. On the other hand, when the cross-sectional area of a cross-section of the honeycomb unit 11′ vertical to the longitudinal direction exceeds 50 cm2, the strength against thermal stress generated in the honeycomb unit 11′ becomes insufficient.
Except for the honeycomb units 11′ located in an outer circumferential portion of the honeycomb structure 10′, the shape of the honeycomb unit 11′ is not limited to a rectangular column shape, and examples thereof include a hexagonal column shape and the like.
Meanwhile, the honeycomb unit 11′ has the same configuration as the honeycomb unit 11 except for the cross-sectional area of a cross-section vertical to the longitudinal direction and the shape.
The thickness of the adhesion layer 13 is preferably in a range of 0.5 mm to 2.0 mm. When the thickness of the adhesion layer 13 is less than 0.5 mm, the adhesion strength of the honeycomb unit 11′ becomes insufficient. On the other hand, when the thickness of the adhesion layer 13 exceeds 2.0 mm, the pressure loss of the honeycomb structure 10′ increases.
Next, an example of the method for manufacturing the honeycomb structure 10′ will be described. First, similarly to the honeycomb structure 10, rectangular column-shaped honeycomb units 11′ are produced. Next, paste for the adhesion layer is applied to the outer circumferential surfaces of a plurality of the honeycomb units 11′ excluding both end surfaces, the honeycomb units are adhered to each other, then, dried and solidified, thereby producing a collection of the honeycomb units 11′.
The paste for the adhesion layer is not particularly limited, and examples thereof include mixtures of an inorganic binder and inorganic particles, mixtures of an inorganic binder and an inorganic fiber, mixtures of an inorganic binder, inorganic particles and an inorganic fiber, and the like.
The inorganic binder contained in the paste for the adhesion layer is not particularly limited, examples thereof include solid content contained in a silica sol, an alumina sol or the like, and two or more inorganic binders may be jointly used. Among the above, the solid content contained in silica sol is preferable.
A material that configures the inorganic particles contained in the paste for the adhesion layer is not particularly limited, examples thereof include carbides such as silicon carbide, nitrides such as silicon nitride and boron nitride, and the like, and two or more inorganic particles may be jointly used. Among the above, silicon carbide is preferable due to the excellent thermal conductivity.
A material that configures the inorganic fiber contained in the paste for the adhesion layer is not particularly limited, examples thereof include silica alumina, mullite, alumina, silica and the like, and two or more inorganic fibers may be jointly used. Among the above, alumina is preferable.
In addition, the paste for the adhesion layer may further contain an organic binder.
The organic binder contained in the paste for the adhesion layer is not particularly limited, examples thereof include polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and the like, and two or more organic binders may be jointly used.
The paste for the adhesion layer may further contain a balloon that is a minute hollow sphere of an oxide-based ceramic, a pore-forming agent and the like.
The balloon contained in the paste for the adhesion layer is not particularly limited, examples thereof include alumina balloons, glass micro balloons, shirasu balloons, fly ash balloons, mullite balloons and the like, and two or more balloons may be jointly used. Among the above, alumina balloons are preferable.
The pore-forming agent contained in the paste for the adhesion layer is not particularly limited, examples thereof include spherical acrylic particles, graphite and the like, and two or more pore-forming agents may be jointly used.
Next, the collection of the honeycomb units 11′ is cut into a circular column shape, and then ground as necessary, thereby producing a circular column-shaped collection of the honeycomb units 11′.
Meanwhile, instead of cutting the collection of the honeycomb units 11′ into a circular column shape, it is also possible to adhere the honeycomb units 11′ to honeycomb units having a predetermined cross-sectional shape vertical to the longitudinal direction, thereby producing a circular column-shaped collection of the honeycomb units.
Next, paste for outer circumference coating layers is applied to the outer circumferential surfaces of the circular column-shaped collection of the honeycomb units 11′ excluding both end surfaces.
The paste for outer circumference coating layers may be the same as or different from the paste for the adhesion layer.
Next, the circular column-shaped collection of the honeycomb units 11′ to which the paste for outer circumference coating layers has been applied is dried and solidified, thereby producing a circular column-shaped honeycomb structure 10′. At this time, in a case in which the paste for the adhesion layer and/or the paste for outer circumference coating layers contain the organic binder, the paste is preferably defatted. The defatting conditions can be appropriately selected depending on the kinds and amounts of organic substances, and the paste is preferably defatted at 600° C. for 1 hour.
Meanwhile, the honeycomb structures 10, 10′ and 10″ may not have the outer circumference coating layer 12 formed therein.
In the present examples, ‘parts’ refer to ‘parts by mass’.
An aqueous solution of phosphoric acid with a concentration of 85% by mass (9.8 parts), an aqueous solution of aluminum hydroxide with a concentration of 95% by mass (7.0 parts), a silica sol containing 30% by mass of a solid content (5.5 parts) and morpholine (11.3 parts) as a structure directing agent were sequentially added to water, and stirred, thereby obtaining a precursor gel. Next, the precursor gel was sealed in an autoclave (200 ml), heated to 200° C. at a temperature-rise rate of 5° C./minute while being mixed at a mixing rate of 10 rpm, and held for 24 hours, thereby producing silicoaluminophosphate particles. Furthermore, as a result of crushing the silicoaluminophosphate particles so as to obtain an average diameter of original silicoaluminophosphate particles of 3.0 μm, and then treating the silicoaluminophosphate particles in an ammonia aqueous solution with a concentration of 5% by mass for 30 minutes, the ratio of the amount of Si to the sum of the amounts of Al and P was 0.16, the specific surface area was 290 m2/g, and the acid point was 1.44 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 1 except that the silicoaluminophosphate particles were treated in the ammonia aqueous solution with a concentration of 5% by mass for 10 minutes. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.16, the specific surface area was 380 m2/g, and the acid point was 1.86 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 1 except that the addition amount of the silica sol containing 30% by mass of a solid content was changed to 6.8 parts. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.20, the specific surface area was 274 m2/g, and the acid point was 1.81 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 3 except that the silicoaluminophosphate particles were treated in the ammonia aqueous solution with a concentration of 5% by mass for 10 minutes. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.20, the specific surface area was 355 m2/g, and the acid point was 2.32 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 1 except that the addition amount of the silica sol containing 30% by mass of a solid content was changed to 8.5 parts. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.25, the specific surface area was 220 m2/g, and the acid point was 1.32 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 5 except that the silicoaluminophosphate particles were treated in the ammonia aqueous solution with a concentration of 5% by mass for 10 minutes. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.25, the specific surface area was 312 m2/g, and the acid point was 1.70 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 1 except that the silicoaluminophosphate particles were not treated in the ammonia aqueous solution with a concentration of 5% by mass. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.16, the specific surface area was 460 m2/g, and the acid point was 1.96 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 5 except that the silicoaluminophosphate particles were not treated in the ammonia aqueous solution with a concentration of 5% by mass. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.25, the specific surface area was 435 m2/g, and the acid point was 1.89 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 1 except that the silicoaluminophosphate particles were treated in the ammonia aqueous solution with a concentration of 5% by mass for 60 minutes. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.16, the specific surface area was 190 m2/g, and the acid point was 1.18 mmol/g.
Silicoaluminophosphate particles were produced in the same manner as in Example 5 except that the silicoaluminophosphate particles were treated in the ammonia aqueous solution with a concentration of 5% by mass for 120 minutes. The ratio of the amount of Si to the sum of the amounts of Al and P was 0.25, the specific surface area was 175 m2/g, and the acid point was 1.13 mmol/g.
The ratio of the amount of Si to the sum of the amounts of Al and P in the silicoaluminophosphate particles was measured using a silicon drift energy dispersive X-ray detector XFlash5030 (manufactured by Bruker Corporation).
The plot of the adsorption amount V [cm3(STP)·g−1] with respect to the relative pressure P/P0, that is, the nitrogen adsorption and desorption isotherm was produced using an automatic surface area and porosimetry analyzer TriStar-3000 (manufactured by Shimadzu Corporation), and the specific surface area of the silicoaluminophosphate particles was obtained using a BET multipoint method. Specifically, the specific surface area was obtained from the plot of P/V(P0−P) [g·cm3(STP)−1] with respect to the relative pressure P/P0, that is, a BET plot.
The acid point of the silicoaluminophosphate particles was measured using a fully automatic temperature-programmed desorption spectrometer apparatus TPD-1-ATw (manufactured by Bel Japan Inc.). Specifically, first, the silicoaluminophosphate particles (0.05 g) were heated to 500° C. at a temperature-rise rate of 10° C./minute, held for 60 minutes, cooled to 300° C., and made to be in a steady state. In this state, ammonia was introduced for 30 minutes so as to make the silicoaluminophosphate particles adsorb the ammonia, then, the ammonia was exhausted, and the silicoaluminophosphate particles were held for 30 minutes. Next, the silicoaluminophosphate particles were heated to 600° C. at a temperature-rise rate of 10° C./minute while introducing helium at 50 ml/minute. The amount of the ammonia desorbed during the above process was determined by detecting the peak of NH2+(m/z=16) using a quadrupole mass spectrometer, and the acid point of the silicoaluminophosphate particles was computed.
The average diameter of original silicoaluminophosphate particles was measured using a laser diffraction particle size distribution analyzer MAS5001 (manufactured by Malvern Instruments Ltd.).
First, the silicoaluminophosphate particles of each of the examples and the comparative examples were immersed in a copper nitrate aqueous solution, thereby being ion-exchanged with copper ions. As a result of measuring the amount of the silicoaluminophosphate particles exchanged with the copper ions by carrying out ICP atomic emission spectrometry using an ICPS-8100 (manufactured by Shimadzu Corporation), the amount was 2.7% by mass.
The silicoaluminophosphate particles ion-exchanged with the copper ions (3000 parts), boehmite (1190 parts), an alumina fiber having an average fiber diameter of 6 μm and an average fiber length of 100 μm (720 parts), methyl cellulose (290 parts), oleic acid (310 parts) and ion exchange water (1820 parts) were mixed and kneaded, thereby producing raw material paste.
Next, the raw material paste was extruded using an extruder, thereby producing a honeycomb compact having a fan-like column shape. In addition, the honeycomb compact was dried at 110° C. for 10 minutes using a microwave dryer and a hot air dryer, thereby producing a dried honeycomb. Furthermore, the honeycomb compact was defatted at 400° C. for 5 minutes, thereby producing a defatted honeycomb. Next, the defatted honeycomb was fired at 700° C. for 2 hours, thereby producing a honeycomb unit. The honeycomb unit has a fan-like column shape with a radius of 132 mm, a center angle of 90° and a length of 76.2 mm, the thickness of a partition wall was 0.20 mm, and the density of through holes was 124 holes/cm2.
Meanwhile, an alumina fiber having an average fiber diameter of 6 μm and an average fiber length of 100 μm (767 parts), silica glass (2500 parts), carboxymethyl cellulose (17 parts), a silica sol containing 30% by mass of a solid content (600 parts), a polyvinyl alcohol (167 parts) and an aluminum balloon (17 parts) were mixed and kneaded, thereby producing paste for the adhesion layer.
The paste for the adhesion layer was applied to the outer circumferential surface of the honeycomb unit excluding end surfaces so that the thickness of the adhesion layer 13 becomes 1.0 mm, four honeycomb units are adhered to each other, then, dried and solidified at 150° C. for 10 minutes, thereby producing a circular column-shaped collection of the honeycomb units.
Furthermore, the paste for the adhesion layer was applied to the outer circumferential surface of the collection of the honeycomb units excluding end surfaces so that the thickness of the outer circumference coating layer 12 becomes 1.0 mm, then, the paste for the adhesion layer was dried, solidified at 150° C. for 10 minutes using a microwave dryer and a hot air dryer, and defatted at 600° C. for 1 hour, thereby producing a honeycomb structure.
Whether cracking occurred in the honeycomb unit was visually evaluated. Meanwhile, a case in which cracking occurred was determined to be X, and a case in which cracking did not occur was determined to be O.
From the honeycomb unit, a circular column-shaped test specimen with a diameter of 25.4 mm and a length of 76.2 mm was cut using a diamond cutter.
The amount of NOx flowing out of the test specimen was measured using an automotive exhaust gas measuring apparatus MEXA-6000FT (manufactured by Horiba, Ltd.) while flowing a 200° C.-hot simulant gas into the test specimen at a space velocity (SV) of 80000/h, and the purification rate [%] of NOx represented by a formula
(the inflow amount of NOx−the outflow amount of NOx)/(the inflow amount of NOx)×100
was computed.
Meanwhile, the space velocity (SV) refers to the ratio of the flow rate [m3/h] of the simulant gas to the apparent volume [m3] of the test specimen, and the simulant gas contains nitrogen monoxide at a concentration of 350 ppm, ammonia at a concentration of 350 ppm, oxygen at a concentration of 10%, water at a concentration of 5% and carbon dioxide at a concentration of 5% with a balance of nitrogen.
Table 1 describes the evaluation results of the specific surface areas and acid points of the silicoaluminophosphate particles of Examples 1 to 6 and Comparative Example 1 to 4, whether cracking occurred in the honeycomb structures, and the NOx purification rates of the honeycomb structures.
It is found from Table 1 that the silicoaluminophosphate particles of Examples 1 to 6 have a specific surface area in a range of 220 m2/g to 380 m2/g and an acid point in a range of 1.32 mmol/g to 2.32 mmol/g, and, in the honeycomb structure produced using the silicoaluminophosphate particles of Examples 1 to 6, cracking did not occur in the honeycomb units. Therefore, it is considered that the silicoaluminophosphate particles of Examples 1 to 6 can suppress the occurrence of cracking in the honeycomb units which is induced by water adsorption-caused contraction or water desorption-caused expansion. In addition, it is found that, since the honeycomb structure produced using the silicoaluminophosphate particles of Examples 1 to 6 have a NOx purification rate in a range of 85% to 93%, the NOx purification performance is excellent.
On the other hand, it is found that the silicoaluminophosphate particles of Comparative Examples 1 and 2 have a specific surface area in a range of 435 m2/g to 460 m2/g, and, in the honeycomb structure produced using the silicoaluminophosphate particles of Comparative Examples 1 and 2, cracking occurred in the honeycomb units. Therefore, it is considered that the silicoaluminophosphate particles of Comparative Examples 1 and 2 cannot suppress the occurrence of cracking in the honeycomb units which is induced by water adsorption-caused contraction or water desorption-caused expansion.
In addition, it is found that, since the silicoaluminophosphate particles of Comparative Examples 3 and 4 have an acid point in a range of 1.13 mmol/g to 1.18 mmol/g, and the honeycomb structure produced using the silicoaluminophosphate particles of Comparative Examples 3 and 4 have an NOx purification rate in a range of 73% to 75%, the NOx purification performance degrades.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2011/068706 | 8/18/2011 | WO | 00 | 12/20/2013 |
