CN1288781A - Method of in-situ synthesizing ferrierite on lumpy cordierite honeycomb ceramic carrier - Google Patents
Method of in-situ synthesizing ferrierite on lumpy cordierite honeycomb ceramic carrier Download PDFInfo
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- CN1288781A CN1288781A CN 99120818 CN99120818A CN1288781A CN 1288781 A CN1288781 A CN 1288781A CN 99120818 CN99120818 CN 99120818 CN 99120818 A CN99120818 A CN 99120818A CN 1288781 A CN1288781 A CN 1288781A
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- organic amine
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Abstract
The method for in-situ synthesizing magnesium-alkali SiO2 zeolite on the blocky iolite honey ceramic carrier includes the following steps: uniformly coating a layer of gel solution containing Al2O3 and Na2O on the surface of carrier, then crystallizing the coated carrier for 3-10 days at 150-200 deg.C under the condition of organic amine and water mixed saturated steam pressure to make magnesium-alkali zeolite in-situ grow on surface of carrier in the mode of gas-solid phase conversion. The described organic amine is selected from ethylenediamine, trieghylamine and pentazane, and the mole ratio of organic amine and water is 1:(0.5-10). Said invention is applicable to virious carriers with different shapes, its coating is uniform and firm, and does not produce environmental pollution.
Description
The invention provides a kind of on the block honeycomb ceramic carrier of cordierite the method for in-situ synthesizing ferrierite.
The support type zeolite molecular sieve is with its high mechanical properties, low pressure drop, and good heat and mass transfer performance is increasingly extensive in the application in petrochemical industry and environmental protection field.Such as the membrane reactor that is used for the petrochemical industry separation process, be used to eliminate the catalytic converter of vehicle exhaust, all the zeolite molecular sieve of working load on various different carriers is as the main component of catalyst.The load zeolite molecular sieve generally has two kinds of methods, and a kind of is dip coating (washcoat), is about to the carrier immersion and contains in the slurries of zeolite molecular sieve, thereby make carrier surface load one deck zeolite molecular sieve.Patent JP0418914, JP07132230 are to use the dip-coating technology at ceramic honey comb area load one deck Cu-ZSM-5 molecular sieve, are used to eliminate vehicle exhaust.JP0847644 uses the dip-coating technology to be used to eliminate vehicle exhaust at ceramic honey comb area load zeolite molecular sieve and other oxide.Though it is even that dip coating has dip-coating, simple to operate, the advantage of wide adaptability, but it is insecure with combining of carrier surface that its critical defect is the dip-coating layer, under some harsh reaction condition, such as the high temperature thermal shocking of vehicle exhaust, molecular sieve layer is easy to peel off from carrier surface, thereby greatly reduces its catalytic performance.The method of another kind of load molecular sieve is original position synthetic technology (insitusynthesis), and the original position of promptly carrying out molecular sieve on carrier surface is synthetic, thereby makes carrier surface one deck molecular sieve crystal of growing securely.Patent USP4800187 uses the original position synthetic technology to synthesize multiple molecular sieve on the ceramic honey comb surface, patent USP4904518 has synthesized ZSM-5 in the silicon chip surface hydro-thermal, ZSM-11, ZSM-12, multiple molecular sieve such as ZSM-20, but the hydro-thermal synthetic technology that above-mentioned patent is used has individual shortcoming, is exactly that molecular sieve is grown inhomogeneously at carrier surface, especially when support shapes is complicated, as hole count greater than 300cells/inch
2Ceramic honey comb or foamed ceramics, the shortcoming of hydro-thermal synthetic technology is just more obvious.
The purpose of this invention is to provide a kind of on lumpy cordierite honeycomb ceramic carrier the method for in-situ synthesizing ferrierite.This method dip-coating is evenly firm, applicable to the carrier of different shape, and does not produce environmental pollution.
The invention provides a kind of on lumpy cordierite honeycomb ceramic carrier the synthetic magnesium alkali SiO of original position
2The method of zeolite at first contains Al at the even dip-coating one deck of carrier surface
2O
3, and Na
2The coagulant liquid of O is characterized in that: the carrier after the dip-coating was depressed crystallization 3～10 days at 150～200 ℃ the organic amine and the mixing saturated vapor of water, make ferrierite with the mode growth in situ of gas-solid inversion of phases in carrier surface; Described organic amine is selected from ethylenediamine, triethylamine, and pyrrolidines, the mol ratio of organic amine and water is 1: (0.5～10).
The gel composition that is used as lotion among the present invention can be mol ratio Al
2O
3: (3～15) SiO
2: (1～10) Na
2O: (500～6000) H
2O.
Because a series of chemical change has taken place in crystallization process of the present invention, carrier surface combines very firmly with the ferrierite layer, has kept the uniformity of dip coating simultaneously again.The mother liquor that organic amine and water are formed is reusable, both conservations, the environmental pollution of having avoided waste liquor to cause again.
Below by example to method afford further instruction of the present invention.
Embodiment 1
With volume is 5ml, 400cells/inch
2Block honeycomb ceramic carrier at 80 ℃ down with the HNO of 1N
3Solution-treated 1h spends deionised water then to neutral.120 ℃ of dry 6h, 500 ℃ of roasting 3h.
With 1.8801gAl
2(SO
4)
3.18H
2O is dissolved in and gets solution 1 in the 15ml water.6.4320g being dissolved in, Ludox gets solution 2 in the 15ml water.Solution 2 is slowly splashed into must coagulant liquid in the solution 1.In addition 1.1280g NaOH is dissolved in the 5ml water, splashes in the above-mentioned coagulant liquid.
The treated block honeycomb ceramic carrier in surface is immersed in the above-mentioned gel for preparing, behind about 5min., take out, hang in the 125ml still with stainless steel wire.6ml ethylenediamine and 6ml water are housed in the bottom of still.After the still sealing, put into 160 ℃ baking oven, crystallization 8 days.After the cooling, take out carrier, be washed till neutrality with deionized water.After the drying, be XRD and characterize.The result is as follows:
2θ d?spacing 100×I/I
0
7.8 11.325 6
9.6 9.205 6
10.4 8.499 100
18.08 4.902 27
18.96 4.676 15
20.8 4.267 4
21.68 4.095 56
22.2 4.001 7
23 3.863 12
23.68 3.754 8
25.52 3.487 10
26.36 3.378 58
27.76 3.211 2
28.4 3.14 67
29.44 3.031 74
32.8 2.728 4
33.88 2.643 22
36.76 2.442 6
37.16 2.417 4
38.52 2.335 11
39.52 2.278 4 The above results proof carrier is made up of cordierite and pure ferrierite.Analyze through ESEM (SEM), prove that the carrier surface layer thickness of having grown is about the ferrierite of 20 μ.Make breaking test with sharp device, it is very firm that the result shows that ferrierite combines with carrier surface, even carrier itself is destroyed, zeolite layer of growth can not split away off on it.
Embodiment 2
The processing of carrier surface and the preparation of gel are just the same with embodiment 1, and difference is the bottom of the synthesis reactor 2ml ethamine of packing into, 4ml ethylenediamine, 6ml water.Its XRD result proves carrier by cordierite, and ferrierite and small amount of impurities are formed.ESEM is the result show, is about 10 μ at the thickness of the epontic ferrierite layer of cordierite.
Embodiment 3
The processing of carrier surface and the preparation of gel are just the same with embodiment 1, and difference is the bottom of the synthesis reactor 6ml pyrrolidines of packing into, 6ml water.Its XRD result proves that carrier is made up of cordierite and ferrierite, does not have other impurity to generate.
Embodiment 4
Other condition is just the same with embodiment 1, and just the liquid phase part in the still is reused the liquid phase that embodiment 1 usefulness is crossed.Its XRD result shows, carrier surface one deck ferrierite of having grown.
Embodiment 5
Other condition is just the same with embodiment 2, and just the liquid phase part in the still is reused the liquid phase that embodiment 2 usefulness are crossed.Its XRD result shows, carrier surface one deck ferrierite of having grown.
Embodiment 6
Other condition and embodiment 3 are identical, and just the liquid phase part in the still is reused the liquid phase that embodiment 3 usefulness are crossed.The carrier that obtains characterizes through XRD, proves carrier surface one deck ferrierite of having grown.
Embodiment 7
With volume is 5m1,400cells/inch
2Block honeycomb ceramic carrier at 80 ℃ down with 10% H
2O
2Solution-treated lh then uses 10%NH
4Cl solution-treated 1h spends deionised water then to neutral.120 ℃ of dry 6h, 500 ℃ of roasting 3h.The preparation of gel and dip-coating are identical with embodiment 1.Its XRD result shows, the cordierite superficial growth one deck ferrierite.Stereoscan photograph shows that the thickness of ferrierite layer is about 30 μ.
Embodiment 8
Other condition is just the same with embodiment 3, and just crystallization temperature is 150 ℃, XRD result has proved cordierite superficial growth one deck ferrierite.
Claims (2)
1. synthetic magnesium alkali SiO of original position on lumpy cordierite honeycomb ceramic carrier
2The method of zeolite at first contains Al at the even dip-coating one deck of carrier surface
2O
3, and Na
2The coagulant liquid of O is characterized in that: the carrier after the dip-coating was depressed crystallization 3～10 days at 150～200 ℃ the organic amine and the mixing saturated vapor of water, make ferrierite with the mode growth in situ of gas-solid inversion of phases in carrier surface; Described organic amine is selected from ethylenediamine, triethylamine, and pyrrolidines, the mol ratio of organic amine and water is 1: (0.5～10).
According to claim 1 described on lumpy cordierite honeycomb ceramic carrier the synthetic magnesium alkali SiO of original position
2The method of zeolite is characterized in that: the gel as lotion consists of mol ratio Al
2O
3: (3～15) SiO
2: (1～10) Na
2O: (500～6000) H
2O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99120818 CN1116112C (en) | 1999-09-22 | 1999-09-22 | Method of in-situ synthesizing ferrierite on lumpy cordierite honeycomb ceramic carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99120818 CN1116112C (en) | 1999-09-22 | 1999-09-22 | Method of in-situ synthesizing ferrierite on lumpy cordierite honeycomb ceramic carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1288781A true CN1288781A (en) | 2001-03-28 |
| CN1116112C CN1116112C (en) | 2003-07-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99120818 Expired - Fee Related CN1116112C (en) | 1999-09-22 | 1999-09-22 | Method of in-situ synthesizing ferrierite on lumpy cordierite honeycomb ceramic carrier |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905145A (en) * | 2010-09-15 | 2010-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN105457667A (en) * | 2015-11-12 | 2016-04-06 | 复榆(张家港)新材料科技有限公司 | Zeolite molecular sieve catalyst for n-butene skeletal isomerization and preparation method thereof |
| CN106809850A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of synthetic method of little crystal grain FER molecular sieve |
-
1999
- 1999-09-22 CN CN 99120818 patent/CN1116112C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905145A (en) * | 2010-09-15 | 2010-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN101905145B (en) * | 2010-09-15 | 2012-11-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN105457667A (en) * | 2015-11-12 | 2016-04-06 | 复榆(张家港)新材料科技有限公司 | Zeolite molecular sieve catalyst for n-butene skeletal isomerization and preparation method thereof |
| CN105457667B (en) * | 2015-11-12 | 2018-04-13 | 复榆(张家港)新材料科技有限公司 | Zeolite molecular sieve catalyst of n-butene skeletal isomerization and preparation method thereof |
| CN106809850A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of synthetic method of little crystal grain FER molecular sieve |
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| Publication number | Publication date |
|---|---|
| CN1116112C (en) | 2003-07-30 |
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