JPH08119766A - Porous ceramic sintered compact and its production - Google Patents

Abstract

PURPOSE: To obtain a porous ceramic sintered compact excellent in chemical durability, heat resistance and rigidity, etc., by selecting sintered compact of a composition containing each prescribed amount of a waste catalyst which was used for fluidized bed catalytic cracking and a binder. CONSTITUTION: A sintered compact of a composition containing 20-90wt.% of a waste catalyst (e.g. silica-alumina waste catalyst) which was used for fluidized bed catalytic cracking, 10-80 pts.wt. of a binder (e.g. kibushi powder soil) and as necessary, 5-25wt.% of a sintering accelerator (e.g. limestone) are selected. The sintered compact is obtained by forming a mixture obtained by mixing a waste catalyst for fluidized bed catalytic cracking, as necessary, previously calcined at 900-1450 deg.C with a binder and water, drying the formed material and baking the formed material at 1000-1500 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a building material, a structural material, a heat-resistant material, which effectively utilizes a fluid catalytic cracking waste catalyst which is an industrial waste.
The present invention relates to a porous ceramic sinter that is suitable as a soundproof material.

[0002]

2. Description of the Related Art A conventional porous ceramic sinter is composed of aggregate particles forming a skeleton and a binder connecting them. Generally, aggregate particles such as feldspar, porcelain stone, and silica are used as a main raw material, and a binder such as clay is added to this as a raw material.
As a sintering accelerator, calcareous is further added with cellulose, polyvinyl, higher alcohol, wax, a binder component such as resin, water retention such as glycerin and stearic acid emulsion, a lubricant, and the like, followed by molding, drying and sintering. It is made of porous ceramic sinter.

The manufacturing process of the porous ceramic sinter is similar to the general ceramic manufacturing process. That is, first,
The main raw materials such as feldspar, porcelain stone, silica stone, cerben and the like and binder such as clay and limestone are crushed separately and dried, and then the particle size is classified according to the application. The respective classified raw materials are mixed, dried and crushed at a ratio according to the purpose and application. Then, a binder, a water retention agent, or a foaming agent as needed is added and kneaded. Then, it is molded by an extrusion molding method, a press molding method, a casting molding method or the like, dried and fired to obtain a porous ceramic sinter.

At this time, particular attention is paid to the shape and average particle size of the aggregate particles, the particle size distribution, the type of binder and the amount added in order to control the pore structure.

First, the properties required for the aggregate of the preferred porous ceramics are analyzed. (1) The heat resistance and the corrosion resistance are excellent. (2) The grain shape is close to spherical. (3) The predetermined grain size range. In order to satisfy these conditions, the raw material preparation process is extremely complicated, and countermeasures against it are strongly required.

On the other hand, the waste catalysts such as alumina-silica and zeolite used in the catalytic cracking unit in the petroleum refining process are partially used as fillers for cement,
Most of them are disposed of as industrial waste for a fee. Looking at the amount of waste catalyst discharged from the catalytic cracking unit in an attempt, an apparatus for treating vacuum gas oil treats 1 ton / day of atmospheric distillation residue with respect to the throughput of 30,000 barrels / day. With a 1,000 barrel / day machine, it reaches a huge amount of 13 tons / day. Moreover, this is an example of one refinery, and it is a surprising amount when the total amount of waste catalyst from the devices existing in refineries nationwide is seen. Therefore, providing new uses for this spent catalyst has become an urgent task.

The composition of the fluid catalytic cracking catalyst in a new stage is a mixture of silica-alumina or zeolite having alumina as a matrix. Generally, these precursors (gel-like substances) are granulated by a spray drying method. The specific surface area is 200 to 30
The average particle size is 0 m ² / g or more and the average particle size is 80 to 100 μm. This new catalyst repeats the cycle of being involved in the reaction and then being regenerated in the catalytic cracking apparatus, and is discharged as a waste catalyst to the outside of the apparatus when the decomposition activity is lowered. 100 m ² / g, average particle size is 6
It changes to around 0μ. The reduction of the specific surface area of the catalyst is to reduce the carbon deposited on the surface of the catalyst in the device system from 680 to 77.
This is because the catalyst composition causes sintering due to the combustion temperature at that time, because the catalyst composition is burned and removed at 0 ° C. to be regenerated. Further, the decrease in the catalyst particle size is due to shrinkage due to sintering and abrasion due to mutual contact between particles during fluid circulation in the apparatus system.

The inventor of the present invention, mysteriously, satisfies the strict conditions (1) to (3) required for the aggregate of the above-mentioned porous ceramic porcelain strangely. I realized that I was doing it. That is, alumina-silica suitable for the aggregate of the porous ceramics sintered body or zeolite having alumina as a matrix contains silica showing heat resistance in any of the waste catalysts, and the corrosion resistance is Is contained, and the shape of the spent catalyst has a spherical shape, and the particle size thereof is in the range of 40 to 70 μm as the average particle size and 10 as the particle size.
˜110 μm, and the catalyst is regenerated and the waste catalyst is sintered by receiving heat of 680 to 770 ° C. and its density is increased. (This also shows good dimensional stability during sintering. Is meant). Therefore, these waste catalysts satisfy the preferable requirements without any modification in manufacturing the porous ceramics.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel porous ceramic sinter using a waste catalyst of fluid catalytic cracking and a method for producing the same.

[0010]

The present invention provides (a) 20 to 90% by weight of fluid catalytic cracking waste catalyst, preferably 50 to 80% by weight, and (b) 10 to 80% by weight of binder, preferably 20. ~ 5
It relates to a porous ceramic sinter, which is a sintered body of a composition containing 0% by weight.

The binder is an inorganic binder, a typical one is clay, and clay for ceramics is preferable. It is preferable to classify these clays to 75 μ or less before use. Examples of the clay include Shigaraki Suihi clay, Kibushi powder soil, Huangose clay, Hagi earth, porcelain earth, Kurita earth and mixed clays thereof.

In the present invention, it is preferable to use a sintering accelerator (melting agent) in combination with the binder. Examples of sintering accelerators include limestone, kaolin, magnesite, wood ash, vinegar ash, sodium bicarbonate, calcium carbonate, magnesium carbonate, bone ash, soda ash and mixtures thereof. It is also preferable to classify these sintering accelerators (melting agents) to 75 μ or less before use.

When this sintering accelerator (melting agent) is blended, (a) 20 to 90% by weight of fluid catalytic cracking waste catalyst, preferably 50 to 80% by weight, (b) 10 to 80% by weight of binder, Preferably 20-50
% By weight (c) Sintering accelerator (melting agent) 3 to 25% by weight, preferably 6 to 15% by weight.

The catalytic cracking waste catalyst can be classified, but has a particle size distribution that can be sufficiently used without classification.

The method for producing the porous ceramic sinter will be described below. First, a binder and, if necessary, a sintering accelerator are added without classifying or classifying a predetermined amount of waste catalyst, and they are sufficiently mixed by a stirring mixer. Then 40-6
Add water in the range of 0 wt% and knead. Next, take the formwork,
It is pressure-molded under normal pressure or a pressure of 50 kg / cm ² or less or higher, or is molded into a predetermined shape by extrusion molding or the like.

The sample after molding is dried at room temperature or vacuum and then at 120 ° C. for 2 to 5 hours, and the temperature is in the range of 1000 to 1500 ° C., preferably 1250 to 1450 ° C., using an electric furnace with a heating program. 2 in the atmosphere in the range of
It is fired for ~ 5 hours to obtain a porous ceramic sinter.

The molded product molded by the above-mentioned operation has a size of 10 to 15% after baking from that at the time of molding because of the amount of clay and water content at the time of molding, and the volume change due to the sintering of the waste catalyst.
Decrease. However, in this respect, it is possible to sufficiently control the influence of shrinkage by strictly controlling the raw material management and the sintering conditions.

On the other hand, in order to minimize the shrinkage of the waste catalyst due to sintering, which is related to the dimensional changes during molding and firing, the waste catalyst is preliminarily stored in an electric furnace or the like in an atmosphere of 900 times.
It is preferable to perform calcination in the range of ˜1450 ° C. for 2 to 5 hours. By calcining the waste catalyst using this as an aggregate, the specific surface area becomes 0.1 to 0.06 m ² / g,
It is close to the geometric surface area. True specific gravity is 2.3-2.
5 g / cm ³ , average sphericity of particles is 1.05 to 1.25
Is. In the classified particles, the sphericity tends to decrease as the particle size increases. The average particle size is 25 to 60 μm, and the particle size distribution is such that it is usually within the range of 10 to 100 μm.

A method for producing a porous ceramic sinter using the thus-preliminarily-calcined waste catalyst as a raw material will be described below. First, a predetermined amount of the calcined waste catalyst is added without adding classification or classification, and clay and a sintering accelerator are added, and they are sufficiently mixed with a stirring mixer. Next, 40 to 60 wt% of water is added to the mixture and kneaded. Next, put it in a mold and press it with normal pressure or press,
It is formed into a predetermined shape by molding or extrusion molding.

The molded sample is dried at room temperature or vacuum, and then dried at 120 ° C. for 2 to 5 hours, and the temperature is in the range of 1000 to 1500 ° C., preferably 1250 to 1450 ° C., using an electric furnace equipped with a heating program. 2 to 2 under atmospheric atmosphere
It is fired for 5 hours to obtain a porous ceramic sinter.

The porous ceramic sinter obtained by this method shows almost no change in volume when the compact is dried, as compared with the case where the waste catalyst is directly used as an aggregate, and the volume due to sintering Effect of change on dimensional formability is 1
It falls within the range of -10% and shows favorable results.

The apparent specific gravity of the porous ceramic sinter obtained according to the present invention is in the range of 1.5 to 2.5 g / cm ³ , and the porosity measured by a Mercury polon meter is 10 to 40%. Yes, bending strength by mechanical universal testing machine (Shimadzu Autograph) is 130-300kg
It showed f / cm ² .

The kerosene refineries, gas oil, NiO-MoO used in hydrodesulfurization of heavy oil _{3 -γAl 2} O _3, Co
If necessary, a waste catalyst of a catalyst having the same or similar composition as that of a fluid catalytic cracking catalyst such as an O-MoO ₃ -γAl ₂ O ₃ -based waste catalyst and having Ni, Co or Mo supported thereon may be used. It can be used by mixing with the waste catalyst. In this case, the considerations regarding the particle size, particle size distribution, and dimensional stability are the same as for the fluid catalytic cracking waste catalyst. Ni
-A mixture of Mo-based waste catalyst has a yellowish color and C
A mixture of o-Mo waste catalysts develops blue color,
The color band of the color change remarkably changes depending on the concentration of Co added. Further, in the desulfurization system waste catalyst, organometallic compounds existing in the raw material depending on the type of raw material oil to be treated, namely vanadium porphyrin, vanadium demetalized by decomposition of nickel porphyrin, nickel, etc. are deposited on the catalyst. As vanadium pentoxide, vanadium effectively acts as a melting agent or a crystallization agent during sintering, and MoO ₃ which is an active metal species also has the same action. On the other hand, regarding the waste catalyst from the fluidized bed catalytic cracker described above, when an organometallic compound is contained in the treated feed oil, in order to prevent catalyst poisoning by the organometallic, antimony pentoxide of several ppm is used as a passivator. It may be added in the order, but it also acts advantageously as a melting agent and a crystallization agent.

[0024]

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 The silica-alumina waste catalyst used in the fluid catalytic cracking apparatus was used as an aggregate. Unclassified silica-alumina waste catalyst and Kibushi powder soil of 75 μm or less were weighed at a weight ratio of 6: 4, mixed for 20 minutes with a mixing stirrer, added with 60 wt% of pure water, and kneaded for 30 minutes with a kneader. It was placed in a stainless steel mold having a length of 100 mm, a width of 50 mm, and a depth of 10 mm, and molded under normal pressure. After molding, dry at room temperature for one day and then 120
After drying at ℃ for 3 hours, the temperature was raised in an electric furnace at a rate of 200 ℃ / 1 hour, and baked and sintered at 1350 ℃ for 3 hours. After cooling to room temperature, the apparent specific gravity, porosity, shrinkage, and bending strength were measured. The results were as follows. Apparent specific gravity 2.12 Porosity (%) 34.4 Shrinkage rate (%) * 16.5 Bending strength (kgf / cm ² ) 225 No cracking or deformation was observed. * Indicates how much the dimensions during molding shrink after firing.

Example 2 A USY zeolite waste catalyst having an alumina matrix used in a fluid catalytic cracking apparatus was used as an aggregate. Waste catalyst classified to 75μ or less and Kibushi powder soil of 75μ or less were weighed in a weight ratio of 6: 4, mixed for 20 minutes by a mixing stirrer, added with 50 wt% of pure water, and kneaded for 30 minutes by a kneader. .
It is placed in a stainless steel mold with a length of 100 mm, a width of 50 mm, and a depth of 50 mm, and is 10 kg / cm ² by a hydraulic press.
Was molded to a thickness of 10 mm. The molded product taken out of the mold is naturally dried at room temperature for one day and then at 120 ° C for 3 days.
Dried for hours. Then, the temperature was raised in an electric furnace at a rate of 200 ° C./1 hour, and the mixture was baked and sintered at 1350 ° C. for 3 hours.
After cooling to room temperature, apparent specific gravity, porosity, shrinkage and
The bending strength was measured. The results were as follows. Apparent specific gravity 2.21 Porosity (%) 31.7 Shrinkage (%) 10.6 Bending strength (kgf / cm ² ) 210 It should be noted that cracks and deformation were not observed in the manufactured porous ceramic sinter. It was

Example 3 The waste zeolite catalyst used in Example 2 was used as an aggregate. Without sieving this aggregate, the grain soil of less than 75μ,
And limestone classified to 75μ or less are weighed at a weight ratio of 60%, 35%, and 5%, and mixed in a dry box for 20 minutes by a mixing stirrer, and pure water 50w
t% was added, and the mixture was kneaded for 30 minutes with a kneader. This is put in a stainless steel mold having a length of 100 mm, a width of 50 mm, and a depth of 50 mm, and the thickness is 1 at 30 kg / cm ² by a hydraulic press.
It was molded to 0 mm. The molded product taken out from the mold is air dried at room temperature for one day and then at 120 ° C for 3 hours.
Dried in oven. Then, it was fired and sintered at 1350 ° C. for 3 hours in an air atmosphere in an electric furnace. After cooling to room temperature, apparent specific gravity, porosity, shrinkage and bending strength were measured. The results were as follows. Apparent specific gravity 2.27 Porosity (%) 30.8 Shrinkage (%) 9.7 Bending strength (kgf / cm ² ) 189 No cracking or deformation was observed in the manufactured porous ceramic sinter. It was

Example 4 The silica-alumina waste catalyst used in Example 1 was used as an aggregate. First, put a certain amount of waste catalyst in a porcelain crucible, and
After drying at 20 ° C. for 2 hours, the temperature was raised in an electric furnace at a rate of 200 ° C./1 hour, and firing was performed at 1200 ° C. for 4 hours in the air atmosphere. After cooling to room temperature, it was classified and the aggregate having a size of 60 μm or less was used. The waste catalyst pretreated in this way and 75μ
The following Kibushi powder soil and limestone of 75μ or less were weighed in a weight ratio of 60%, 35% and 5%, and mixed in a dry box for 20 minutes by a mixing stirrer, and then pure water 47 wt% Was added and kneaded for 30 minutes with a kneader. Length 100mm, width 50mm, depth 50mm
50kg by hydraulic press
It was molded to a thickness of 10 mm at / cm ² . The molded product taken out of the mold was dried at room temperature for a whole day and night, and further at 120 ° C. for 3 hours. Then, using an electric furnace, 145
It was baked and sintered at 0 ° C. for 3 hours. After cooling to room temperature, apparent specific gravity, porosity, shrinkage and bending strength were measured. The results were as follows. Apparent specific gravity 2.34 Porosity (%) 27.3 Shrinkage (%) 5.6 Bending strength (kgf / cm ² ) 189 No cracking or deformation was observed.

Example 5 The zeolite waste catalyst used in Example 2 was used as an aggregate. First, a predetermined amount of waste catalyst was placed in a porcelain crucible, dried at 120 ° C. for 2 hours, heated in an electric furnace at a rate of 200 ° C./1 hour, and calcined at 1250 ° C. for 4 hours in an air atmosphere. After cooling to room temperature, without classifying it, yellow sand clay classified to a particle size of 75μ or less and limestone classified to a particle size of 75μ or less are reduced to 65%, 30%, or 5% by weight, respectively. Weigh and mix 2 in a dry box with a mixer.
After mixing for 0 minutes, 45 wt% of pure water was added, and the mixture was kneaded for 30 minutes by a kneader. Length 100mm, width 50
mm and a depth of 50 mm, and placed in a stainless steel mold, and formed into a thickness of 10 mm with a hydraulic press at 50 kg / cm ² .
The molded product taken out of the mold was dried at room temperature for a whole day and night, and further at 120 ° C. for 3 hours. Then, it was fired and sintered at 1450 ° C. for 4 hours in an electric atmosphere in an electric furnace.
After cooling to room temperature, apparent specific gravity, porosity, shrinkage and bending strength were measured. The results were as follows. Apparent specific gravity 2.36 Porosity (%) 25.4 Shrinkage rate (%) 4.8 Bending strength (kgf / cm ² ) 236 No cracking or deformation was observed in the sintered body.

The pore distribution of each sintered body of this example was measured by a Mercury Polonometer (manufactured by Shimadzu Corporation), and as a result, all of them showed a sharp mountain shape which was normally distributed between the pore diameters of 1 μ to 10 μ. The pore size at the 50% point was in the range of 2.1 to 3.5μ.

The embodiments of the present invention will be listed below. 1. A porous ceramic sinter which is a composition containing (a) 20 to 90% by weight of a fluid catalytic cracking waste catalyst and (b) 10 to 80% by weight of a binder. 2. It is a sintered body of a composition containing (a) fluid catalytic cracking waste catalyst 20 to 90% by weight (b) binder 10 to 80% by weight (c) sintering accelerator 5 to 25% by weight. And porous ceramics. 3. Apparent specific gravity 1.5 to 2.5 g / cm ³ , porosity 10 to 40 measured by Mercury polon meter
%, The porous ceramic sinter according to item 1 or 2, which has a bending strength of 130 to 300 kgf / cm ² measured by a mechanical universal testing machine (Autograph manufactured by Shimadzu Corporation). 4. The porous ceramic sinter according to the above 1, 2, or 3, containing a Ni—Mo waste catalyst. 5. The porous ceramic sinter according to the above 1, 2, or 3, containing a Co—Mo based waste catalyst. 6. A method for producing a porous ceramic sinter, which comprises molding a mixture containing a fluidized catalytic cracking waste catalyst, a binder and water, drying and firing at 1000 to 1500 ° C. 7. The fluid catalytic cracking waste catalyst is preliminarily calcined at 900 to 1450 ° C, and a mixture obtained by mixing the binder and water is molded and dried, and then 1000 to 1500 ° C.
A method for producing a porous ceramic sinter, which is characterized by firing at.

[0032]

[Effect] The sintered body obtained by the present invention has chemical durability,
Because it has excellent properties such as heat resistance and rigidity, it is used as a filter for gas, liquid, etc., catalyst carrier, adsorbent, sound absorbing material, heat insulating agent, building material, etc. in the industrial fields such as chemical industry as well as food and medicine. Have. This allows industrial waste to be reused as a useful resource. Further, according to the present invention, the selection work, the classification work, the granulation process and the like regarding the granularity of the aggregate can be significantly shortened as compared with the conventional method using the aggregate.

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[Procedure amendment]

[Submission date] February 14, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

The inventor of the present invention, mysteriously, satisfies the strict conditions (1) to (3) required for the aggregate of the above-mentioned porous ceramic porcelain strangely. I realized that I was doing it. That is, alumina-silica suitable for the aggregate of the porous ceramics sintered body or zeolite having alumina as a matrix contains silica showing heat resistance in any of the waste catalysts, and the corrosion resistance is Is contained, and the shape of the spent catalyst has a spherical shape, and the particle size thereof is in the range of 40 to 70 μm as the average particle size and 10 as the particle size.
˜110 μm, and the catalyst is regenerated and the waste catalyst is sintered by receiving heat of 680 to 770 ° C. and its density is increased. (This also shows good dimensional stability during sintering. Is meant). Therefore, these waste catalysts have preferable requirements without any modification in producing the porous ceramic sinter.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

The embodiments of the present invention will be listed below. 1. A porous ceramic sinter which is a composition containing (a) 20 to 90% by weight of a fluid catalytic cracking waste catalyst and (b) 10 to 80% by weight of a binder. 2. It is a sintered body of a composition containing (a) fluid catalytic cracking waste catalyst 20 to 90% by weight (b) binder 10 to 80% by weight (c) sintering accelerator 5 to 25% by weight. Porous ceramic sinter. 3. Apparent specific gravity 1.5 to 2.5 g / cm ³ , porosity 10 to 40 measured by Mercury polon meter
%, The porous ceramic sinter according to item 1 or 2, which has a bending strength of 130 to 300 kgf / cm ² measured by a mechanical universal testing machine (Autograph manufactured by Shimadzu Corporation). 4. The porous ceramic sinter according to the above 1, 2, or 3, containing a Ni—Mo waste catalyst. 5. The porous ceramic sinter according to the above 1, 2, or 3, containing a Co—Mo based waste catalyst. 6. A method for producing a porous ceramic sinter, which comprises molding a mixture containing a fluidized catalytic cracking waste catalyst, a binder and water, drying and firing at 1000 to 1500 ° C. 7. The fluid catalytic cracking waste catalyst is preliminarily calcined at 900 to 1450 ° C, and a mixture obtained by mixing the binder and water is molded and dried, and then 1000 to 1500 ° C.
A method for producing a porous ceramic sinter, which is characterized by firing at.

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Claims (4)

[Claims] 1. A porous ceramic ware which is a sintered body of a composition containing (a) 20 to 90% by weight of a fluid catalytic cracking waste catalyst and (b) 10 to 80% by weight of a binder. Union. 2. A sintered body of a composition containing (a) 20 to 90% by weight of a fluid catalytic cracking waste catalyst, (b) 10 to 80% by weight of a binder, and (c) 5 to 25% by weight of a sintering accelerator. Porous ceramics characterized by being. 3. A mixture containing a fluid catalytic cracking waste catalyst, a binder and water is molded and dried, and then 1000 to 1500.
A method for producing a porous ceramics sintered body, which comprises firing at ℃. 4. A fluidized catalytic cracking waste catalyst containing 900 to 1450
Preliminarily calcined at ℃, mix this with a binder and water to form a mixture, and after drying, 1000 to 1
A method for producing a porous ceramics sintered body, which comprises firing at 500 ° C.