CN109133860B - Honeycomb ceramic catalyst carrier and preparation method thereof - Google Patents
Honeycomb ceramic catalyst carrier and preparation method thereof Download PDFInfo
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- CN109133860B CN109133860B CN201811185651.7A CN201811185651A CN109133860B CN 109133860 B CN109133860 B CN 109133860B CN 201811185651 A CN201811185651 A CN 201811185651A CN 109133860 B CN109133860 B CN 109133860B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 42
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 29
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003063 flame retardant Substances 0.000 claims abstract description 22
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 22
- 239000000454 talc Substances 0.000 claims abstract description 22
- 229910052623 talc Inorganic materials 0.000 claims abstract description 22
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 20
- 239000005350 fused silica glass Substances 0.000 claims abstract description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 17
- 239000001923 methylcellulose Substances 0.000 claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 17
- 239000003549 soybean oil Substances 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims description 18
- 235000010981 methylcellulose Nutrition 0.000 claims description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
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- 238000010304 firing Methods 0.000 abstract description 41
- 238000000034 method Methods 0.000 abstract description 20
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 238000012797 qualification Methods 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/32—Burning methods
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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Abstract
The invention belongs to the technical field of honeycomb ceramic materials, and particularly relates to a honeycomb ceramic catalyst carrier and a preparation method thereof. The honeycomb ceramic catalyst carrier disclosed by the invention takes alumina, magnesia, fused quartz, talc and raw kaolin as inorganic main materials, and is added with methylcellulose, a bromobenzene flame retardant, an organic silicon polyether copolymer, soybean oil and water as catalysts, particularly a low-smoke and low-toxicity bromobenzene flame retardant, so that the honeycomb ceramic catalyst carrier is a functional auxiliary agent for endowing a flammable polymer with flame retardancy, can provide the flame retardancy of a high-molecular material, can effectively inhibit the combustion of organic matters in the honeycomb ceramic carrier, avoids the temperature difference between the inside and the outside of the carrier, and improves the sintering qualification rate; meanwhile, the inhibition effect of the flame retardant can quickly raise the temperature of the honeycomb ceramic carrier in the firing process, which is beneficial to improving the production efficiency and has the advantages of energy conservation and environmental protection.
Description
Technical Field
The invention belongs to the technical field of honeycomb ceramic materials, and particularly relates to a honeycomb ceramic catalyst carrier and a preparation method thereof.
Background
Increasingly stringent emissions regulations have made exhaust aftertreatment systems standard parts for automobiles and ships. The exhaust aftertreatment system converts pollutants carbon monoxide CO, hydrocarbons HC and nitrogen oxides NOx in engine exhaust gas into harmless carbon dioxide CO using a catalyst with redox capability2Nitrogen gas N2And water H2And O, enabling the tail gas to meet the emission standard.
In the prior art, a honeycomb ceramic material-supported catalyst (catalyst carrier) is mostly used in an exhaust gas aftertreatment system for a motor vehicle or a ship to treat pollutants, such as a Selective Catalytic Reduction (SCR) catalyst carrier, an oxidation catalytic conversion (DOC) catalyst carrier, a three-way catalyst (TWC) catalyst carrier for a gasoline vehicle, and the like. The existing honeycomb ceramic carrier preparation process route is mainly 'mixing, kneading, pugging, ageing, screening, forming, drying, cutting, firing, edging and surrounding edge'. In the process of mixing, organic matters such as a binder (such as cellulose ether), a dispersant (such as alcohol ether) and a lubricant (such as high-quality oil) are generally required to be added, so that the content of the organic matters in the raw materials for preparing the catalyst exceeds 9 percent. In the firing process of the honeycomb ceramic carrier, as the honeycomb ceramic is internally provided with tens of thousands of blank spaces, the decomposition of organic matters contained in the honeycomb ceramic and the heat transfer generated in the combustion process are limited, so that the internal temperature of the honeycomb ceramic carrier is far higher than the external temperature, a larger radial temperature gradient is formed, thermal stress is generated, the honeycomb ceramic is easy to crack due to unreasonable temperature control of a firing kiln, and the firing qualified rate is reduced.
In order to solve the problem, the temperature rise rate of an organic matter volatilization section in a firing temperature curve is strictly controlled at present, and the radial temperature field distribution of the honeycomb ceramic carrier is reasonably controlled so as to avoid cracking of the honeycomb ceramic carrier in the firing process, but even if the temperature rise rate is controlled to be 95% only by counting the product qualification rate of the traditional honeycomb ceramic carrier firing process. The too low temperature rise rate of the organic matter volatilization section leads the firing period of the honeycomb ceramic carrier to be long, which seriously restricts the improvement of the production efficiency of the production line, and simultaneously, the great consumption of fuel and the firing waste products lead the reduction of the production cost of the honeycomb ceramic carrier to be difficult. Therefore, it is required to develop a honeycomb ceramic catalyst carrier that can realize rapid firing to ensure the yield and production efficiency of products.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a honeycomb ceramic catalyst carrier, so as to solve the problems of low qualified rate and overlong firing cycle of the finished honeycomb ceramic catalyst carrier in the prior art;
the second technical problem to be solved by the present invention is to provide a method for preparing the above honeycomb ceramic catalyst carrier.
In order to solve the technical problems, the raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
18-22 wt% of alumina;
3-5 wt% of magnesium oxide;
12-18 wt% of fused quartz;
25-30 wt% of talc;
30-35 wt% of raw kaolin;
the additive comprises nitrogen flame retardant accounting for 0.5 to 2.0 weight percent of the total weight of the inorganic main material.
Preferably, the addition amount of the nitrogen-based flame retardant accounts for 1.5 wt% of the total amount of the inorganic main material.
The honeycomb ceramic catalyst carrier comprises the following inorganic main materials in percentage by mass:
20.17 wt% of alumina;
4.11 wt% of magnesium oxide;
15.24 wt% of fused quartz;
talc 27.12 wt%;
raw kaolin 33.36 wt%.
Preferably, the honeycomb ceramic catalyst carrier further comprises the following components in mass content based on the total amount of the inorganic main materials:
3-5 wt% of methyl cellulose;
0.2-0.8 wt% of organic silicon polyether copolymer;
0.5-1.5 wt% of soybean oil.
Preferably, the honeycomb ceramic catalyst carrier further comprises the following components in percentage by mass based on the total amount of the inorganic main materials:
4 wt% of methyl cellulose;
0.5 wt% of silicone polyether copolymer;
1 wt% of soybean oil.
The alumina is D50-10-30 μm, and the diameter-thickness ratio is 2-8: 1, a tabular alumina;
the magnesium oxide is high-activity magnesium oxide with the D50 being 1.0-3.0 mu m;
d50 of the fused quartz is 2.0-6.0 um;
the talc is platy talc with D50 being 10-30 um;
the raw kaolin has a D50 of 4-8 μm.
The honeycomb ceramic catalyst carrier includes an SCR, DOC, ASC or TWC honeycomb ceramic catalyst carrier, i.e., including but not limited to a selective catalytic reduction SCR catalyst carrier, an oxidation catalytic converter DOC catalyst carrier, a three-way catalyst TWC catalyst carrier, and the like.
The invention also discloses a method for preparing the honeycomb ceramic catalyst carrier, which comprises the following steps:
(1) taking selected amounts of the alumina, the magnesia, the fused quartz, the talc, the raw kaolin, the methylcellulose, the bromobenzene flame retardant and the organic silicon polyether copolymer, and fully mixing in a dry way to obtain mixed powder;
(2) adding soybean oil and water into the obtained mixed powder for kneading, performing vacuum pugging treatment, extruding into a honeycomb ceramic catalyst carrier with a required size, and drying to obtain a blank;
(3) and firing the obtained green body by using the honeycomb ceramic catalyst carrier to obtain a finished product.
In the step (3), the temperature control process of the firing step of the honeycomb ceramic catalyst carrier includes:
after the reaction is started, controlling the reaction temperature to rise to 140-160 ℃ at the temperature rise rate of 45-55 ℃/h;
then controlling the reaction temperature to be raised to 580-620 ℃ at the temperature raising rate of 45-55 ℃/h;
then controlling the reaction temperature to raise to 980-1020 ℃ at the temperature raising rate of 45-55 ℃/h;
then controlling the reaction temperature to raise to 1080-;
then controlling the reaction temperature to rise to 1180-1220 ℃ at a temperature rise rate of 90-110 ℃/h;
then controlling the reaction temperature to be 1410-1420 ℃ at the heating rate of 25-35 ℃/h;
then carrying out the incubation reaction at 1410-1420 ℃ for 7-9 h.
In the step (2), the addition amount of the water accounts for 30-40 wt% of the total amount of the inorganic main materials.
In the step (2), the size of the honeycomb ceramic catalyst carrier is phi 330.2X (101.6-203.2) mm, 400-600 holes/square inch and the wall thickness is 3-4 mil.
The honeycomb ceramic catalyst carrier disclosed by the invention takes alumina, magnesia, fused quartz, talc and raw kaolin as inorganic main materials, and is added with methylcellulose, a bromobenzene flame retardant, an organic silicon polyether copolymer, soybean oil and water as catalysts, particularly a low-smoke and low-toxicity bromobenzene flame retardant, so that the honeycomb ceramic catalyst carrier is a functional auxiliary agent for endowing a flammable polymer with flame retardancy, can provide the flame retardancy of a high-molecular material, can effectively inhibit the combustion of organic matters in the honeycomb ceramic carrier, avoids the temperature difference between the inside and the outside of the carrier, and improves the sintering qualification rate; meanwhile, the inhibition effect of the flame retardant can quickly raise the temperature of the honeycomb ceramic carrier in the firing process, which is beneficial to improving the production efficiency and has the advantages of energy conservation and environmental protection.
According to the preparation method of the honeycomb ceramic catalyst carrier, the honeycomb ceramic catalyst carrier is manufactured according to the technological process of mixing, kneading, pugging, screening, forming, shaping, drying, cutting and firing, the yield of the prepared honeycomb ceramic is close to 100% by controlling the temperature gradient in the firing process, the time of the whole firing process is greatly shortened, and the production efficiency is effectively improved.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a graph showing temperature control in the firing step in examples 1 to 3 of the present invention;
FIG. 2 is a graph showing the temperature control in the firing step in comparative example 1 of the present invention.
Detailed Description
The temperature control curve of the honeycomb ceramic catalyst carrier in the firing process is shown in figure 1, and specifically comprises the following steps:
after the reaction is started, controlling the reaction temperature to rise to 140-160 ℃ at the temperature rise rate of 45-55 ℃/h;
then controlling the reaction temperature to be raised to 580-620 ℃ at the temperature raising rate of 45-55 ℃/h;
then controlling the reaction temperature to raise to 980-1020 ℃ at the temperature raising rate of 45-55 ℃/h;
then controlling the reaction temperature to raise to 1080-;
then controlling the reaction temperature to rise to 1180-1220 ℃ at a temperature rise rate of 90-110 ℃/h;
then controlling the reaction temperature to be 1410-1420 ℃ at the heating rate of 25-35 ℃/h;
then carrying out the incubation reaction at 1410-1420 ℃ for 7-9 h.
The temperature control curve of the firing process of the traditional honeycomb ceramic catalyst carrier in the prior art is shown in fig. 2, and specifically comprises the following steps:
after the reaction is started, controlling the reaction temperature to rise to 140-160 ℃ at the temperature rise rate of 45-55 ℃/h;
then controlling the reaction temperature to be raised to 580-620 ℃ at the temperature raising rate of 5-15 ℃/h;
then controlling the reaction temperature to raise to 980-1020 ℃ at the temperature raising rate of 45-55 ℃/h;
then controlling the reaction temperature to raise to 1080-;
then controlling the reaction temperature to rise to 1180-1220 ℃ at a temperature rise rate of 90-110 ℃/h;
then controlling the reaction temperature to be 1410-1420 ℃ at the heating rate of 15-25 ℃/h;
then carrying out the incubation reaction at 1410-1420 ℃ for 7-9 h.
Example 1
The raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
d50 ═ 20 μm and the aspect ratio was 4:1 flake alumina 20.17 wt%;
4.11 wt% of high-activity magnesium oxide with the D50 being 2.0 mu m;
15.24 wt% of fused quartz with D50 being 4.0 um;
27.12 wt% of platy talc with D50 ═ 15 um;
33.36 wt% of raw kaolin with the diameter of 6 mu m as D50;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
1.5 wt% of decabromodiphenylethane flame retardant;
4 wt% of methyl cellulose;
0.5 wt% of silicone polyether copolymer;
1 wt% of soybean oil;
35 wt% of water.
The preparation method of the honeycomb ceramic catalyst carrier described in this embodiment includes the following steps:
(1) according to the selected materials, 20.17kg of alumina, 4.11kg of magnesia, 15.24kg of fused quartz, 27.12kg of talc, 33.36kg of raw kaolin, 4kg of methyl cellulose, 1.5kg of decabromodiphenylethane flame retardant and 0.5kg of organic silicon polyether copolymer are taken and fully dry-mixed to obtain mixed powder;
(2) adding 1kg of soybean oil and 35kg of water into the obtained mixed powder for conventional kneading, performing vacuum pugging treatment, extruding into a honeycomb ceramic catalyst carrier with phi of 330.2 multiplied by 152.4mm, 400 holes per square inch and 4mil of wall thickness, and performing conventional drying treatment at 90-130 ℃ for more than 10 hours to obtain a blank;
(3) and (3) firing the obtained green body according to the rapid firing curve designed in the following table 1 to obtain the finished product.
TABLE 1 green body firing Curve
Example 2
The raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
20.17 wt% of flake alumina having a diameter-thickness ratio of 4:1 and D50 of 20 μm;
4.11 wt% of high-activity magnesium oxide with the D50 being 2.0 mu m;
15.24 wt% of fused quartz with D50 being 4.0 um;
27.12 wt% of platy talc with D50 ═ 15 um;
33.36 wt% of raw kaolin with the diameter of 6 mu m as D50;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
0.5 wt% of brominated epoxy resin flame retardant;
4 wt% of methyl cellulose;
0.5 wt% of silicone polyether copolymer;
1 wt% of soybean oil;
35 wt% of water.
The preparation method of the honeycomb ceramic catalyst carrier described in this embodiment includes the following steps:
(1) according to the selected materials, 20.17kg of alumina, 4.11kg of magnesia, 15.24kg of fused quartz, 27.12kg of talc, 33.36kg of raw kaolin, 4kg of methylcellulose, 0.5kg of decabromodiphenyl ether flame retardant and 0.5kg of organic silicon polyether copolymer are taken and fully dry-mixed to obtain mixed powder;
(2) adding 1kg of soybean oil and 35kg of water into the obtained mixed powder for conventional kneading, performing vacuum pugging treatment, extruding into a honeycomb ceramic catalyst carrier with phi of 330.2 multiplied by 152.4mm, 400 holes per square inch and 4mil of wall thickness, and performing conventional drying treatment at 90-130 ℃ for more than 10 hours to obtain a blank;
(3) and (3) firing the obtained green body according to the rapid firing curve designed in the table 1 to obtain the finished product of the honeycomb ceramic catalyst carrier.
Example 3
The raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
d50 ═ 20 μm and the aspect ratio was 4:1 flake alumina 20.17 wt%;
4.11 wt% of high-activity magnesium oxide with the D50 being 2.0 mu m;
15.24 wt% of fused quartz with D50 being 4.0 um;
27.12 wt% of platy talc with D50 ═ 15 um;
33.36 wt% of raw kaolin with the diameter of 6 mu m as D50;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
brominated polystyrene flame retardant 2.0 wt%;
4 wt% of methyl cellulose;
0.5 wt% of silicone polyether copolymer;
1 wt% of soybean oil;
35 wt% of water.
The preparation method of the honeycomb ceramic catalyst carrier described in this embodiment includes the following steps:
(1) according to the selected materials, 20.17kg of alumina, 4.11kg of magnesia, 15.24kg of fused quartz, 27.12kg of talc, 33.36kg of raw kaolin, 4kg of methyl cellulose, 2.0kg of decabromodiphenylethane flame retardant and 0.5kg of organic silicon polyether copolymer are taken and fully dry-mixed to obtain mixed powder;
(2) adding 1kg of soybean oil and 35kg of water into the obtained mixed powder for conventional kneading, performing vacuum pugging treatment, extruding into a honeycomb ceramic catalyst carrier with phi of 330.2 multiplied by 152.4mm, 400 holes per square inch and 4mil of wall thickness, and performing conventional drying treatment at 90-130 ℃ for more than 10 hours to obtain a blank;
(3) and (3) firing the obtained green body according to the rapid firing curve designed in the table 1 to obtain the finished product of the honeycomb ceramic catalyst carrier.
Example 4
The raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
d50 ═ 20 μm and the aspect ratio was 4: 18 wt% of flake alumina of 1;
d50 ═ 2.0 μm of high-activity magnesium oxide 5 wt%;
12 wt% of fused quartz with the thickness of D50 ═ 4.0 um;
30 wt% of platy talc with D50 of 15 um;
d50 ═ 6 μm raw kaolin 35 wt%;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
decabromodiphenylethane flame retardant 0.5 wt%;
3 wt% of methyl cellulose;
0.8 wt% of silicone polyether copolymer;
0.5 wt% of soybean oil;
40 wt% of water.
The preparation method of the honeycomb ceramic catalyst carrier of this example is the same as that of example 1.
Example 5
The raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
d50 ═ 20 μm and the aspect ratio was 4:1 flake alumina 22 wt%;
d50 ═ 2.0 μm of high-activity magnesium oxide 5 wt%;
18 wt% of fused quartz with D50 being 4.0 um;
25 wt% of platy talc with D50 ═ 15 um;
d50 ═ 6 μm of raw kaolin 30 wt%;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
2.0 wt% of nitrogen flame retardant;
5 wt% of methyl cellulose;
0.2 wt% of silicone polyether copolymer;
1.5 wt% of soybean oil;
30 wt% of water.
The preparation method of the honeycomb ceramic catalyst carrier of this example is the same as that of example 1.
Example 6
The raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
d50 ═ 20 μm and the aspect ratio was 4:1, 20 wt% of flake alumina;
3 wt% of high-activity magnesium oxide with the D50 being 2.0 mu m;
17 wt% of fused quartz with D50 being 4.0 um;
28 wt% of platy talc with D50 ═ 15 um;
d50 ═ 32 wt% of 6 μm raw kaolin;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
brominated epoxy resin flame retardant 1.5 wt%;
4 wt% of methyl cellulose;
0.5 wt% of silicone polyether copolymer;
1 wt% of soybean oil;
35 wt% of water.
The preparation method of the honeycomb ceramic catalyst carrier of this example is the same as that of example 1.
Comparative example 1
The raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
d50 ═ 20 μm and the aspect ratio was 4:1 flake alumina 20.17 wt%;
4.11 wt% of high-activity magnesium oxide with the D50 being 2.0 mu m;
15.24 wt% of fused quartz with D50 being 4.0 um;
27.12 wt% of platy talc with D50 ═ 15 um;
33.36 wt% of raw kaolin with the diameter of 6 mu m as D50;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
4 wt% of methyl cellulose;
0.5 wt% of silicone polyether copolymer;
1 wt% of soybean oil;
35 wt% of water.
The preparation method of the honeycomb ceramic catalyst carrier described in this embodiment includes the following steps:
(1) according to the selected materials, 20.17kg of alumina, 4.11kg of magnesia, 15.24kg of fused quartz, 27.12kg of talcum, 33.36kg of raw kaolin, 4kg of methyl cellulose and 0.5kg of organic silicon polyether copolymer are taken and fully dry-mixed to obtain mixed powder;
(2) adding 1kg of soybean oil and 35kg of water into the obtained mixed powder for conventional kneading, performing vacuum pugging treatment, extruding into a honeycomb ceramic catalyst carrier with phi of 330.2 multiplied by 152.4mm, 400 holes per square inch and 4mil of wall thickness, and performing conventional drying treatment at 90-130 ℃ for more than 10 hours to obtain a blank;
(3) and firing the obtained green body according to the traditional firing curve designed in the following table 2 to obtain the finished product.
TABLE 5 conventional green body firing curves
Examples of the experiments
1. 1 firing Process parameter testing
The results of measurements of the data such as the product yield in the firing process of the honeycomb ceramics described in examples 1 to 3 and comparative example 1 are shown in table 1 below.
TABLE 1 comparison of firing Process parameter test results
| Numbering | Amount of organic matter/%) | Temperature rise rate/DEG C/h in organic matter decomposition stage | Total firing time/h | Percent of pass/%) | Shrinkage ratio/% |
| Example 1 | 5.5 | 50 | 42.08 | 100 | 0 |
| Example 2 | 5.5 | 50 | 42.08 | 99.5 | 0 |
| Example 3 | 5.5 | 50 | 42.08 | 98.7 | 0 |
| Comparative example 1 | 5.5 | 10 | 78.08 | 92.9 | 0 |
As can be seen from the data in Table 1, the addition of 0.5-2.0% of bromobenzene flame retardant in the honeycomb ceramic catalyst carrier has very significant effects on the temperature rise rate of the organic matter decomposition stage, the total firing time and the product percent of pass in the honeycomb ceramic firing process; the heating rate of the decomposition stage of the organic matter in the firing process of the honeycomb ceramic carrier ceramic can be increased from 10 ℃/h to 50 ℃/h, the total firing time is reduced from 78.08h to 42.08h, the product percent of pass is increased from 92.9% to over 99%, and when the addition amount of the flame retardant is 1.5%, the firing percent of pass of the honeycomb ceramic carrier can reach 100%, so that the honeycomb ceramic carrier ceramic has a remarkable effect.
2. Product performance test of honeycomb ceramic catalyst carrier
The performance of the honeycomb ceramic catalyst carrier products prepared in examples 1 to 3 and comparative example 1 was tested, and the test indexes include thermal expansion coefficient (room temperature-800 ℃), water absorption, compressive strength parallel to the axial direction, and thermal shock resistance, and are recorded in table 2 below.
TABLE 2 Honeycomb ceramics Performance test results
From the data in the table, the performance indexes of the honeycomb ceramic catalyst carrier prepared by the method can reach the level of the existing product, and the performance requirements of the finished product are met.
3. Durability test
The honeycomb ceramic catalyst supports prepared in the above examples 1 to 3 and comparative example 1 were coated with a molecular sieve catalyst (coating amount 200g/l), encapsulated, and subjected to durability tests to examine the durability of the supports and the pollutant-converting ability, and their 50 km engine durability tests were tested and recorded in the following table 3.
TABLE 3 durability test results
| Numbering | Durability | Pollutant discharge |
| Example 1 | No damage and no cracking | Lower than the national VI standard limit value |
| Example 2 | No damage and no cracking | Lower than the national VI standard limit value |
| Example 3 | No damage and no cracking | Lower than the national VI standard limit value |
| Comparative example 1 | No damage and no cracking | Lower than the national VI standard limit value |
From the data in the table, the performance of the honeycomb ceramic catalyst carrier product meets the standard requirement.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. The honeycomb ceramic catalyst carrier is characterized in that raw materials for preparing the honeycomb ceramic catalyst carrier comprise inorganic main materials and additives;
the inorganic main material comprises the following components in percentage by mass in total:
18-22 wt% of alumina;
3-5 wt% of magnesium oxide;
12-18 wt% of fused quartz;
25-30 wt% of talc;
30-35 wt% of raw kaolin;
based on the total amount of the inorganic main materials, the additive comprises the following components in percentage by mass:
0.5 to 2.0 weight percent of nitrogen flame retardant;
3-5 wt% of methyl cellulose;
0.2-0.8 wt% of organic silicon polyether copolymer;
0.5-1.5 wt% of soybean oil.
2. The honeycomb ceramic catalyst carrier according to claim 1, wherein the nitrogen-based flame retardant is added in an amount of 1.5 wt% based on the total amount of the inorganic main material.
3. The honeycomb ceramic catalyst carrier according to claim 1 or 2, wherein the inorganic main material comprises the following components by mass:
20.17 wt% of alumina;
4.11 wt% of magnesium oxide;
15.24 wt% of fused quartz;
talc 27.12 wt%;
raw kaolin 33.36 wt%.
4. The honeycomb ceramic catalyst carrier according to claim 1 or 2, characterized in that:
the alumina is D50-10-30 μm, and the diameter-thickness ratio is 2-8: 1, a tabular alumina;
the magnesium oxide is high-activity magnesium oxide with the D50 being 1.0-3.0 mu m;
d50 of the fused quartz is 2.0-6.0 um;
the talc is platy talc with D50 being 10-30 um;
the raw kaolin has a D50 of 4-8 μm.
5. The ceramic honeycomb catalyst carrier according to claim 1, wherein the ceramic honeycomb catalyst carrier comprises an SCR, DOC, ASC, or TWC ceramic honeycomb catalyst carrier.
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