CN100563828C - A kind of is the manufacture craft of the cellular catalyst carrier of primary raw material with the natural zeolite - Google Patents
A kind of is the manufacture craft of the cellular catalyst carrier of primary raw material with the natural zeolite Download PDFInfo
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- CN100563828C CN100563828C CNB2006100533707A CN200610053370A CN100563828C CN 100563828 C CN100563828 C CN 100563828C CN B2006100533707 A CNB2006100533707 A CN B2006100533707A CN 200610053370 A CN200610053370 A CN 200610053370A CN 100563828 C CN100563828 C CN 100563828C
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- Prior art keywords
- cellular
- catalyst carrier
- finished product
- natural zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 230000001413 cellular effect Effects 0.000 title claims abstract description 29
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000010457 zeolite Substances 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 8
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 7
- 239000001923 methylcellulose Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000011265 semifinished product Substances 0.000 claims abstract description 6
- 238000010792 warming Methods 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 229910052878 cordierite Inorganic materials 0.000 description 8
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011020 iolite Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
A kind of manufacture craft of efficient cellular catalyst carrier is characterized in that natural zeolite is ground into powder, injects watery hydrochloric acid and stirs, and leaves standstill the back and uses the water rinse zeolite powder to neutral; In the zeolite powder, add potter's clay, mixed rare-earth oxide and methylcellulose, mix the back and drop into and fully bondingly in the vacuum pugmill to be squeezed into cellular semi-finished product through mould.Cellular (system) semi-finished product are put into activation furnace, and low temperature drying is warming up to 500 ℃～600 ℃ then, treats that its cooling is the cellular catalyst carrier finished product.Advantage of the present invention is: preparation technology is simple, and expense, energy consumption are low, and the carrier finished product has good adsorption performance and metal cation switching performance, can reduce the use amount of the rare precious metal in the catalyst activity component greatly, improves catalytic conversion.
Description
Technical field
The present invention relates to a kind of manufacture craft of efficient cellular catalyst carrier, particularly a kind of is the manufacture craft of the cellular catalyst carrier of primary raw material with the natural zeolite, and affiliated technical field is making inorganic and that solid material is chemical.
Background technology
Catalyst carrier is the support of catalyst material, coats catalyst material on its surface and forms all kinds of catalytic units with catalyst, is widely used in industries such as chemical industry, environmental protection, heat generating, as automobile exhaust purifier.For improving the performance of catalyst, must enlarge the specific area of carrier, make cellular usually.
At present, cellular catalyst carrier commonly used mostly is with cordierite (Mg on the market
2Al
4Si
5O
18) make for primary raw material.Its primary raw material is a cordierite, in addition talcum powder, potter's clay, commercial alumina etc., and mixed moulding is after high temperature sintering forms the honeycomb substrate skeleton.The catalyst carrier specific area that makes with the method is little, causes later washcoat area little, has influenced catalytic efficiency; Secondly, it does not have activity fully, only provides a secondary skeleton.So for improving its specific area, need, just can be used as carrier and use with the formed body surfaces externally and internally of high-specific surface area material one gamma-alumina coated behind sintering.Aluminium oxide shell coating process is comparatively complicated, need carrier framework repeatedly be impregnated in aluminium oxide suspension and oven dry repeatedly, can be coated with certain thickness (25～50 μ m) and carry in its surface, it is first carrier that the honeycomb substrate of title skeleton is arranged in the industry, the activated alumina shell of coating is second carrier, with cordierite (Mg
2Al
4Si
5O
18) cellular catalyst carrier made is also referred to as two step production methods.
Chinese patent (patent No. ZL01801630.8) has been introduced a kind of method of making cordierite ceramic honeycomb.This method be with cordierite raw material and binder through mixing, extruding, drying, the dried formed body of sintering, thus obtain with the honeycomb structured body of cordierite crystalline phase as principal component.Wherein, in sintering step, maximum temperature reaches 1300 ℃.
Chinese patent (patent No. ZL02130059.3) has been introduced a kind of iolite honeycomb ceramic catalyst that is used for the denitrogenation of flue gas soil and its production and application, it is characterized in that cordierite honeycomb ceramic is coated with activated alumina film, the denitrification catalyst of Supported CuO preparation again.
Above-mentioned patent introduce with cordierite (Mg
2Al
4Si
5O
18) make the cellular catalyst carrier method, be two step production methods, not only operation is numerous and diverse, the production cost height, and aluminum oxide coating layer peels off easily, makes loss of activity, influences result of use and life-span.
Summary of the invention
The purpose of this invention is to provide a kind of production technology of cellular catalyst carrier efficiently.It is simple that production technology of the present invention has operation, and cost, energy consumption are low, easy to operate, the characteristics of constant product quality.
Making cellular catalyst carrier method provided by the present invention is with natural zeolite (M
N/20AlO
3XSiO
2YH
20) be primary raw material, add appropriate amount of auxiliary materials, adopt inorganic synthesis technique, the moulding heating does not need coated aluminium oxide shell, promptly makes the high-specific surface area that can directly use, highly active cellular catalyst carrier.
The invention provides the preparation technical scheme steps that efficient cellular catalyst carrier adopted is:
A, elder generation become particle diameter 150～250 purpose powders with zeolite pulverizing, ball milling, inject the watery hydrochloric acid that molar concentration is 2～5mol/L then, stir, and leave standstill to use the water rinse zeolite powder to neutral after 3～4 hours dry for standby.
B, the zeolite powder handled among the A is added potter's clay (H
2Al
2Si
2O
8), mixed rare-earth oxide, methylcellulose and water for ball milling mix.
C, the mixed powder of gained is put in the vacuum pugmill, made it fully bonding, and deflate, be squeezed into cellular semi-finished product through mould.
D, the cellular semi-finished product of extrusion molding are put into activation furnace, be warming up to 100 ℃～200 ℃ with 4～6 ℃ of/minute heating rates, constant temperature 2～3 hours, oven dry continues to be warming up to 500 ℃～600 ℃ then, is incubated 4～5 hours.Treat that its cooling is the cellular catalyst carrier finished product.
Natural zeolite powder consumption of the present invention (by weight) accounts for 50%～80% of whole raw materials.
The potter's clay consumption (by weight) that the present invention adds accounts for 10%～35%, and mixed rare-earth oxide (by weight) accounts for 3%～10%, and methylcellulose (by weight) accounts for 2%～5%, and water (by weight) accounts for 3%～5%.
Mixed powder is put into the air that carries out in the vacuum pugmill taking out when bonding in the blending bunker among the present invention, and feed bin pressure is not more than 0.6 atmospheric pressure.
Making cellular catalyst carrier method provided by the present invention, the carrier specific surface area of finished products 〉=90m that makes
2/ g, A face can bear pressure
2, the B face can bear pressure and be 〉=15kg/cm
2, proportion is 0.8～0.9g/cm
3, water absorption rate is 18～25%, thermal coefficient of expansion 1.5～1.6 * 10
-6/ ℃.
Making cellular catalyst carrier method provided by the present invention, the carrier finished-product material that makes is M
N/20AlO
3XSiO
2YH
20This material has good adsorption performance and metal cation switching performance, help the dispersion of active component and the combination of active structure, can reduce the use amount (can reduce to 0.3～0.5 ‰) of the rare precious metal in the catalyst activity component greatly, improve catalytic conversion by 1～3 ‰.
The advantage of efficient making cellular catalyst carrier method provided by the present invention is: technology is simple, a step preparation, and cost, energy consumption are low, and specific surface area of finished products is big, the catalyst conversion ratio height that makes.
The specific embodiment
Embodiment 1
200 order zeolite powder 30kg after the watery hydrochloric acid of getting molar concentration and be 2.5mol/L is handled put into mixer, start mixer and add 15kg potter's clay, 4kg mixed rare-earth oxide, 2kg methylcellulose and 2kg water successively, fully mix.Compound is put into vacuum pugmill, and the mould of packing into after mediating repeatedly is squeezed into cellular.Honeycomb ceramics after being shaped is put into activation furnace, be warming up to 100 ℃ and kept this furnace temperature 3 hours with 5 ℃ of/minute heating rates, treat again furnace temperature slowly to be risen to 600 ℃ after its baking parches, constant temperature 4 hours is cooled to room temperature then, little yellow honeycomb substrate.Every index to product is measured, and overall dimensions are 50 * 50 * 50mm
3, channel diameter is 1.5mm, cell densities is 27/cm
2, the duct wall thickness is 0.35～0.40mm, and free cross-sectional area is 65～70%, and specific area is 90～130m
2/ g, A face can bear pressure
2, the B face can bear pressure and be 〉=15kg/cm
2, proportion is 0.8g/cm
3, water absorption rate is 18～25%, thermal coefficient of expansion 1.5 * 10
-6/ ℃.
Embodiment 2/
With with embodiment 1 identical operations, difference be with baking temperature be controlled at 200 ℃ the baking 2 hours.Finally every index of product is measured, gained data parameters index is within control range.
Embodiment 3
With with embodiment 1 identical operations, difference is to adjust the proportioning of each constituent.Get 200 order zeolite powder 40kg after watery hydrochloric acid is handled, potter's clay 10kg, mixed rare-earth oxide 3kg and methylcellulose, each 2kg of water.Finally every index of product is measured, gained data parameters index is within control range.
Claims (2)
1, a kind of preparation method of cellular catalyst carrier is a primary raw material with the natural zeolite, adds appropriate amount of auxiliary materials, adopts inorganic synthesis technique, and the moulding heating makes the high-specific surface area that can directly use, highly active cellular catalyst carrier, and preparation process is:
A, elder generation become particle diameter 150～250 purpose powders with natural zeolite pulverizing, ball milling, inject the watery hydrochloric acid that molar concentration is 2～5mol/L then, stir, and leave standstill to use the water rinse natural zeolite powder to neutral after 3～4 hours dry for standby;
B, the natural zeolite powder handled among the A is added potter's clay, mixed rare-earth oxide, methylcellulose and water for ball milling mix, the consumption of described raw material is by weight: natural zeolite powder accounts for 50%～80%, potter's clay accounts for 10%～35%, mixed rare-earth oxide accounts for 3%～10%, methylcellulose accounts for 2%～5%, and water accounts for 3%～5%;
C, the mixed powder of gained is put in the vacuum pugmill, made it fully bonding, and deflate, be squeezed into cellular semi-finished product through mould;
D, the cellular semi-finished product of extrusion molding are put into activation furnace, be warming up to 100 ℃～200 ℃ with 4～6 ℃ of/minute heating rates, constant temperature 2～3 hours, oven dry, continue to be warming up to 500 ℃～600 ℃ then, be incubated 4～5 hours, treat that its cooling is the cellular catalyst carrier finished product.
2. according to the preparation method of the described cellular catalyst carrier of claim 1, it is characterized in that mixed powder put into and carry out in the vacuum pugmill that the atmospheric pressure in the blending bunker is not more than 0.6 atmospheric pressure when bonding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100533707A CN100563828C (en) | 2006-09-13 | 2006-09-13 | A kind of is the manufacture craft of the cellular catalyst carrier of primary raw material with the natural zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100533707A CN100563828C (en) | 2006-09-13 | 2006-09-13 | A kind of is the manufacture craft of the cellular catalyst carrier of primary raw material with the natural zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1919457A CN1919457A (en) | 2007-02-28 |
| CN100563828C true CN100563828C (en) | 2009-12-02 |
Family
ID=37777376
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100533707A Expired - Fee Related CN100563828C (en) | 2006-09-13 | 2006-09-13 | A kind of is the manufacture craft of the cellular catalyst carrier of primary raw material with the natural zeolite |
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| Country | Link |
|---|---|
| CN (1) | CN100563828C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174089A (en) * | 2018-11-06 | 2019-01-11 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of tourmaline powder carried palladium catalyst |
| CN109301270A (en) * | 2018-11-06 | 2019-02-01 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of high-performance ruthenium catalyst |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103240112B (en) * | 2013-05-03 | 2014-11-05 | 刘光文 | High-performance coal-fired boiler denitration catalyst |
| CN103641507B (en) * | 2013-11-28 | 2015-04-08 | 江苏高淳陶瓷实业有限公司 | Zeolite-attapulgite composite honeycomb body and preparation method thereof |
| EP3253488A1 (en) * | 2015-02-06 | 2017-12-13 | Johnson Matthey Public Limited Company | Three-way catalyst and its use in exhaust systems |
| CN111017949A (en) * | 2019-11-29 | 2020-04-17 | 南通斐腾新材料科技有限公司 | Preparation method of hollow zeolite |
| CN116815552B (en) * | 2023-08-30 | 2023-10-31 | 德州广源环保科技有限公司 | Forming process of honeycomb zeolite module for rotating wheel |
-
2006
- 2006-09-13 CN CNB2006100533707A patent/CN100563828C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174089A (en) * | 2018-11-06 | 2019-01-11 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of tourmaline powder carried palladium catalyst |
| CN109301270A (en) * | 2018-11-06 | 2019-02-01 | 陕西瑞科新材料股份有限公司 | A kind of preparation method of high-performance ruthenium catalyst |
| CN109301270B (en) * | 2018-11-06 | 2021-08-10 | 陕西瑞科新材料股份有限公司 | Preparation method of high-performance ruthenium catalyst |
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| Publication number | Publication date |
|---|---|
| CN1919457A (en) | 2007-02-28 |
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