CN103406139A - Preparation method of molecular sieve integral type catalyst with high mechanical stability - Google Patents
Preparation method of molecular sieve integral type catalyst with high mechanical stability Download PDFInfo
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- CN103406139A CN103406139A CN2013102225880A CN201310222588A CN103406139A CN 103406139 A CN103406139 A CN 103406139A CN 2013102225880 A CN2013102225880 A CN 2013102225880A CN 201310222588 A CN201310222588 A CN 201310222588A CN 103406139 A CN103406139 A CN 103406139A
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Abstract
The invention discloses a preparation method of a molecular sieve integral type catalyst with high mechanical stability, and belongs to the technical field of catalysis. The preparation method comprises the following steps: mixing sodium hydroxide, sodium metaaluminate, silicon sol and deionized water, stirring to form a uniform and stable molecular sieve mother solution; pouring the molecular sieve mother solution into a high-pressure reaction kettle lined with polytetrafluoroethylene, and then placing a cordierite honeycomb ceramic carrier subjected to acid etching pretreatment into the high-pressure reaction kettle; sealing, and then continuously rotating and swinging the high-pressure kettle to react at 160-180 DEG C for 16-48 hours; and taking out, washing, drying at 80-160 DEG C for 1-3 hours, and roasting at 400-600 DEG C for 4-8 hours to prepare the integral type catalyst. According to the preparation method disclosed by the invention, an active material used for preparing the integral type catalyst is firmly adhered with the cordierite honeycomb ceramic carrier, is difficult to desquamate and has high mechanical stability property. The preparation method of the integral type catalyst, which is disclosed by the invention, has the advantages of simple and convenient process, convenience for industrial large-scale production, wide application prospect and the like.
Description
Technical field
The present invention relates to a kind of preparation method of high mechanical stability integral catalyzer, specifically a kind ofly take the preparation method of molecular sieve as the high mechanical stability ceramic honey comb base monolithic catalyst of active material.
Background technology
Integral catalyzer is by the integrated catalyst of many narrow parallel channels proper alignment, usually integral carrier and coating, active component isoreactivity material, is consisted of.Integral carrier is the basic framework of catalyst, common honeycomb ceramic carrier and metallic carrier two classes; Coating is used for increasing the specific area of catalyst, can also strengthen the adhesion property of load active component on integral carrier simultaneously, and itself also has certain catalytic activity some coating.Active component is the key component of integral catalyzer, can provide reaction required catalytic active site.Owing to having the advantages such as bed pressure drop is low, catalytic efficiency is high, enlarge-effect is little, integral catalyzer has been widely used in many fields in recent years, as vehicle exhaust and industrial organic exhaust gas catalytic combustion, natural gas catalytic combustion etc., become in current heterogeneous catalysis field one of the most potential research direction.
Integral catalyzer not only will have higher activity, also will possess stronger mechanical stability.As patent CN1768934A, relate to a kind of purification of volatile organic pollutant by nickel-palladium integral type catalyst and preparation method.This catalyst be take cordierite ceramic and is carrier, cerium-carrying zirconium solid solution, rare earth oxide, aluminium oxide are coating, nickel-palladium metal the oxide of take is active component, prepared catalyst has advantages of that to the catalytic combustion of toluene catalytic combustion efficiency is high and initiation temperature is low, but its mechanical strength is lower, and active component easily comes off.Document (Journal of the American Ceramic Society91 (1) and for example, 2008,64-70) various molecular sieves are made to slurries with aqueous dispersion, then be coated on the honeycomb ceramic integral carrier, system thinking the impact of various preparation factors, but a significant problem is exactly that coated molecular sieve easily comes off from integral carrier.
In a word, adopt traditional infusion process or slurry cladding process carrying active substance on integral carrier, although operation is simple, but active material disperses uneven, easily stop up duct, and, under higher space velocity, because mechanical stability is poor, cause the loss of active component, cause activity decreased in course of reaction, cause secondary pollution.Therefore, a kind of preparation method of simple and easy to do high mechanical stability integral catalyzer is proposed, significant in each field extensive use for integral catalyzer.
Summary of the invention
Goal of the invention: the object of the invention is to, active material appearance caducous problem lower for current integral catalyzer mechanical stability, a kind of preparation method of molecular sieve as the molecular sieve integral catalyzer of a kind of high mechanical stability of active material of take is provided.
Technical scheme: for solving the problems of the technologies described above, the invention provides a kind of preparation method of molecular sieve integral catalyzer of high mechanical stability, the method comprises the steps: NaOH, sodium metaaluminate, Ludox and deionized water are pressed to oxide mol ratio
Sodium oxide molybdena 1～10
Aluminium oxide 1～2
Silica 5～72
Deionized water 10～3000
Mix, at room temperature stirred 4～8 hours, form uniform and stable molecular sieve mother liquor, be poured in the autoclave of inner liner polytetrafluoroethylene, and add pretreated cordierite honeycomb ceramic carrier, after sealing, constantly rotate and swing autoclave, at 160～180 ℃ of reaction 16～48h, take out washing, through 1～3 hour, 400～600 ℃ roastings of 80～160 ℃ of dryings 4～8 hours, make integral catalyzer.
Preferably, described autoclave rotates with swaying movement regularity and is: at first around the autoclave axle, rotated 30 minutes with per minute 10～30 speed that turn, then swing 3 times, constantly repeat this cycle, complete whole course of reaction.
Beneficial effect:
Integral catalyzer preparation method's of the present invention preparation technology is simple, and molecular sieve is combined with carrier firmly, and difficult drop-off does not need follow-up separation process yet, simple to operate.The integral catalyzer specific area that this method is synthesized is larger, can take full advantage of the surfaces externally and internally of molecular sieve.And the molecular sieve catalyst of preparation to have mechanical strength high, function admirable, the advantage such as cheap.
The specific embodiment
Below the present invention will be further described.
It is carrier that the molecular sieve integral catalyzer of the high mechanical stability that the present invention is prepared adopts cordierite honeycomb ceramic carrier, at the synthetic X-type of its passage surfaces externally and internally, Y type, A type, type ZSM 5 molecular sieve.Molecular sieve is 10.1～25.5wt% in the load capacity (with respect to the initial mass of ceramic monolith) on cordierite honeycomb ceramic carrier surface.
Integral catalyzer preparation method of the present invention is: first ,Lv source, silicon source and deionized water are mixed, stir and obtain the molecular sieve mother liquor, then by molecular sieve carried on the carrier cordierite ceramic surface, its detailed process is as follows:
NaOH, sodium metaaluminate, Ludox and deionized water are mixed, vigorous stirring, make uniform and stable molecular sieve mother liquor, the molecular sieve mother liquor obtained is poured in the autoclave of inner liner polytetrafluoroethylene, then the pretreated honeycomb ceramic carrier of acid etching is added wherein, after sealing, constantly rotate and swing autoclave, at 160～180 ℃ of reaction 16～48h, take out washing, after 80～160 ℃ of drying 1～3h, 400～600 ℃ of roasting 4～8h, make integral catalyzer.Synthetic molecular sieve can be X-type, Y type, A type, type ZSM 5 molecular sieve, and each material content (calculating by oxide mol ratio) is: sodium oxide molybdena 1～10, aluminium oxide 1～2, silica 5～72, deionized water 10～3000.
The preparation method of the molecular sieve integral catalyzer of high mechanical stability according to claim 1, it is characterized in that: described autoclave rotates with swaying movement regularity and is: at first around the autoclave axle, rotated 30 minutes with per minute 10～30 speed that turn, then swing 3 times, constantly repeat this cycle, complete whole course of reaction.
Below in conjunction with embodiment, illustrate the preparation method of integral catalyzer, describe simultaneously the test result of the mechanical stability of prepared catalyst, and compare with traditional preparation method, but the present invention is not limited to these embodiment.
Embodiment 1
(1) preparation of ZSM-5 molecular sieve mother liquor
The sodium metaaluminate that takes the NaOH of 0.95g and 0.15g is put into the beaker of 250ml, add in the deionized water of 40ml, treat that it dissolves fully, dropwise add again 20% 15g Ludox, then be placed on magnetic stirring apparatus vigorous stirring 4h at normal temperatures, standing a period of time, form good fluidity, uniform and stable molecular sieve mother liquor, and transfer them in the autoclave of inner liner polytetrafluoroethylene.
(2) preparation of ZSM-5/ cordierite catalyst
Cordierite honeycomb ceramic carrier (forms Mg
2Al
4Si
5O
18, specification is: φ 8 * 24mm, square opening, hole density 400cpsi, wall thickness 0.21mm) in 50% acetum, soak 1h, 600 ℃ of lower roasting 2h after, it is immersed in above-mentioned molecular sieve mother liquor, put into baking oven.After sealing, constantly rotate and swing autoclave and (with per minute 15 speed that turn, rotate 30min around the autoclave axle, then swing 3 times, constantly repeat this cycle), at 170 ℃ of reaction 36h, take out, washing, make the ZSM-5 molecular sieve load capacity and be 16.5% integral catalyzer after 100 ℃ of dry 2h, 500 ℃ of roasting 4h.
(3) mechanical stability evaluation
The mechanical stability evaluation is to carry out in supersonic wave cleaning machine and Muffle furnace.Synthetic ZSM-5/ cordierite catalyst is put into to the test tube that benzinum is housed, after vibration 0.5h, take out at 100 ℃ of dry 1h in supersonic wave cleaning machine, continuous three times, only have 1.4% ZSM-5 molecular sieve to split away off from cordierite honeycomb ceramic carrier.Carry out thermal shock test, roasting 0.5h in 500 ℃, take out suddenly coolingly in air, continues to put into the Muffle furnace roasting again, three times so repeatedly, only has 1.6% ZSM-5 molecular sieve to split away off.
And traditional ZSM-5 molecular sieve powder and appropriate boehmite powder are added to the water, after putting into ball mill rotation 24h, the pretreated honeycomb ceramic carrier of acid etching was added in the molecular sieve slurry 3 minutes, blow away unnecessary part, 100 ℃ of dryings 2 hours, then 500 ℃ of roasting 4h, can repeatedly apply, to obtain and above-mentioned close load capacity, estimate under identical condition with above-mentioned synthetic integral catalyzer.Found that under the condition of supersonic oscillations have 16.4% ZSM-5 molecular sieve to split away off from cordierite honeycomb ceramic carrier, under thermal shock conditions, have 20.2% ZSM-5 molecular sieve to split away off.
Embodiment 2
(1) preparation of Y zeolite mother liquor
The sodium metaaluminate that takes the NaOH of 1.8g and 0.84g is put into the beaker of 250ml, add in the deionized water of 36ml, treat that it dissolves fully, dropwise add again 20% 18g Ludox, then be placed on magnetic stirring apparatus vigorous stirring 4h at normal temperatures, standing a period of time, form good fluidity, uniform and stable molecular sieve mother liquor, and transfer them in the autoclave of inner liner polytetrafluoroethylene.
(2) preparation of Y zeolite/cordierite catalyst
Cordierite honeycomb ceramic carrier (forms Mg
2Al
4Si
5O
18, specification is: φ 8 * 24mm, square opening, hole density 400cpsi, wall thickness 0.21mm) in 50% acetum, soak 1h, 600 ℃ of lower roasting 2h after, it is immersed in above-mentioned molecular sieve mother liquor, put into baking oven.After sealing, constantly rotate and swing autoclave and (with per minute 20 speed that turn, rotate 30min around the autoclave axle, then swing 3 times, constantly repeat this cycle), at 170 ℃ of reaction 36h, take out, washing, make the Y zeolite load capacity and be 15.5% integral catalyzer after 100 ℃ of dry 2h, 500 ℃ of roasting 4h.
(3) mechanical stability evaluation
By the method evaluation of implementing 1, under the condition of supersonic oscillations, there is 1.7% Y zeolite to split away off from cordierite honeycomb ceramic carrier, under the condition of thermal shock, there is 1.8% Y zeolite to split away off.
And traditional cordierite honeycomb ceramic carrier surface that Y zeolite is coated in is estimated under identical condition with above-mentioned synthetic integral catalyzer.Found that under the condition of supersonic oscillations have 17.5% Y zeolite to split away off from cordierite honeycomb ceramic carrier, under thermal shock conditions, have 18.7% Y zeolite to split away off.
Embodiment 3
(1) preparation of X-type molecular sieve mother liquor
The sodium metaaluminate that takes the NaOH of 1.2g and 0.8g is put into the beaker of 250ml, add in the deionized water of 35ml, treat that it dissolves fully, dropwise add again 20% 16g Ludox, then be placed on magnetic stirring apparatus vigorous stirring 4h at normal temperatures, standing a period of time, form good fluidity, uniform and stable molecular sieve mother liquor, and transfer them in the autoclave of inner liner polytetrafluoroethylene.
(2) preparation of X-type molecular sieve/cordierite catalyst
Cordierite honeycomb ceramic carrier (forms Mg
2Al
4Si
5O
18, specification is: φ 8 * 24mm, square opening, hole density 400cpsi, wall thickness 0.21mm) in 50% acetum, soak 1h, 600 ℃ of lower roasting 2h after, it is immersed in above-mentioned molecular sieve mother liquor, put into baking oven.After sealing, constantly rotate and swing autoclave and (with per minute 10 speed that turn, rotate 30min around the autoclave axle, then swing 3 times, constantly repeat this cycle), at 170 ℃ of reaction 36h, take out, washing, make the molecular sieve carried amount of X-type and be 18.5% integral catalyzer after 100 ℃ of dry 2h, 500 ℃ of roasting 4h.
(3) mechanical stability evaluation
By the method evaluation of implementing 1, under the condition of supersonic oscillations, there is 2.1% X-type molecular sieve to split away off from cordierite honeycomb ceramic carrier, under the condition of thermal shock, there is 1.8% X-type molecular sieve to split away off.
And traditional cordierite honeycomb ceramic carrier surface that the X-type molecular sieve is coated in is estimated under identical condition with above-mentioned synthetic integral catalyzer.Found that under the condition of supersonic oscillations have 15.5% X-type molecular sieve to split away off from cordierite honeycomb ceramic carrier, under thermal shock conditions, have 19.7% Y zeolite to split away off.
Embodiment 4
(1) preparation of A type molecular sieve mother liquor
The sodium metaaluminate that takes the NaOH of 1.2g and 1.4g is put into the beaker of 250ml, add in the deionized water of 20ml, treat that it dissolves fully, dropwise add again 20% 16.8g Ludox, then be placed on magnetic stirring apparatus vigorous stirring 4h at normal temperatures, standing a period of time, form good fluidity, uniform and stable molecular sieve mother liquor, and transfer them in the autoclave of inner liner polytetrafluoroethylene.
(2) preparation of A type molecular sieve/cordierite catalyst
Cordierite honeycomb ceramic carrier (forms Mg
2Al
4Si
5O
18, specification is: φ 8 * 24mm, square opening, hole density 400cpsi, wall thickness 0.21mm) in 50% acetum, soak 1h, 600 ℃ of lower roasting 2h after, it is immersed in above-mentioned molecular sieve mother liquor, put into baking oven.After sealing, constantly rotate and swing autoclave and (with per minute 30 speed that turn, rotate 30min around the autoclave axle, then swing 3 times, constantly repeat this cycle), at 170 ℃ of reaction 36h, take out, washing, make the A type molecular sieve load capacity and be 14.4% integral catalyzer after 100 ℃ of dry 2h, 500 ℃ of roasting 4h.
(3) mechanical stability evaluation
By the method evaluation of implementing 1, under the condition of supersonic oscillations, there is 1.5% A type molecular sieve to split away off from cordierite honeycomb ceramic carrier, under the condition of thermal shock, there is 2.4% A type molecular sieve to split away off.
And traditional cordierite honeycomb ceramic carrier surface that A type molecular sieve is coated in is estimated under identical condition with above-mentioned synthetic integral catalyzer.Found that under the condition of supersonic oscillations have 18.5% A type molecular sieve to split away off from cordierite honeycomb ceramic carrier, under thermal shock conditions, have 19.7% A type molecular sieve to split away off.
Can prepare by the present invention take X-type, Y type, A type, type ZSM 5 molecular sieve and is the integral catalyzer of active material, and the active material of prepared integral catalyzer and cordierite honeycomb ceramic carrier adhere to firmly, and difficult drop-off, have the high mechanical stability energy.Integral catalyzer preparation method of the present invention has simple process, is convenient to the advantages such as industrial scale production, has broad application prospects.
From the above embodiments, finding out, the prepared integral catalyzer of the present invention has very high mechanical stability.Simultaneously, integral catalyzer preparation technology of the present invention is simple, is easy to promote, and has broad application prospects.
Claims (2)
1. the preparation method of the molecular sieve integral catalyzer of a high mechanical stability, it is characterized in that: the method comprises the steps: NaOH, sodium metaaluminate, Ludox and deionized water are pressed to oxide mol ratio
Sodium oxide molybdena 1～10
Aluminium oxide 1～2
Silica 5～72
Deionized water 10～3000
Mix, at room temperature stirred 4～8 hours, form uniform and stable molecular sieve mother liquor, be poured in the autoclave of inner liner polytetrafluoroethylene, and add pretreated cordierite honeycomb ceramic carrier, after sealing, constantly rotate and swing autoclave, at 160～180 ℃ of reaction 16～48h, take out washing, through 1～3 hour, 400～600 ℃ roastings of 80～160 ℃ of dryings 4～8 hours, make integral catalyzer.
2. the preparation method of the molecular sieve integral catalyzer of high mechanical stability according to claim 1, it is characterized in that: described autoclave rotates with swaying movement regularity and is: at first around the autoclave axle, rotated 30 minutes with per minute 10～30 speed that turn, then swing 3 times, constantly repeat this cycle, complete whole course of reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106622337A (en) * | 2016-11-28 | 2017-05-10 | 中国石油天然气集团公司 | Alumina carrier modified by Y-zeolite mother liquor and preparation method and application thereof |
| CN107569984A (en) * | 2017-09-30 | 2018-01-12 | 中国化学工程第六建设有限公司 | A kind of method of denitrating flue gas |
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| CN101204665A (en) * | 2006-12-21 | 2008-06-25 | 中国科学院生态环境研究中心 | Integral type catalyst decomposing nitrous oxide and preparation method thereof |
| DE102011010104A1 (en) * | 2010-02-01 | 2011-08-04 | Johnson Matthey Public Ltd. Co. | Three-way catalyst comprising an extruded solid body |
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2013
- 2013-06-04 CN CN2013102225880A patent/CN103406139A/en active Pending
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| CN101204665A (en) * | 2006-12-21 | 2008-06-25 | 中国科学院生态环境研究中心 | Integral type catalyst decomposing nitrous oxide and preparation method thereof |
| DE102011010104A1 (en) * | 2010-02-01 | 2011-08-04 | Johnson Matthey Public Ltd. Co. | Three-way catalyst comprising an extruded solid body |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622337A (en) * | 2016-11-28 | 2017-05-10 | 中国石油天然气集团公司 | Alumina carrier modified by Y-zeolite mother liquor and preparation method and application thereof |
| CN106622337B (en) * | 2016-11-28 | 2019-05-07 | 中国石油天然气集团公司 | A kind of alumina support and the preparation method and application thereof that Y molecular sieve mother liquor is modified |
| CN107569984A (en) * | 2017-09-30 | 2018-01-12 | 中国化学工程第六建设有限公司 | A kind of method of denitrating flue gas |
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Application publication date: 20131127 |