CN103121696B - The synthetic method of ZSM-5 molecular sieve with small crystal grains - Google Patents
The synthetic method of ZSM-5 molecular sieve with small crystal grains Download PDFInfo
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Abstract
The present invention relates to a kind of method of synthesizing small crystal grain ZSM-5-5 molecular sieve, the problem that during the vapor-phase synthesis ZSM-5 molecular sieve mainly existed in solution prior art, crystal grain is excessive.Silicon source, aluminium source and each material of water mix by adopting by the present invention, and obtain jelly mixture, said mixture is 0.001 ~ 1.00kgf in vacuum tightness, and temperature is that under 50 ~ 200 DEG C of conditions, vacuum-drying obtains dry glue; Dry glue is put into the top of crystallizing kettle container, template or its aqueous solution is added above dry glue, at 100 ~ 250 DEG C, crystallization is after 2 ~ 150 hours, obtain the technical scheme of ZSM-5 molecular sieve with small crystal grains, solve this problem preferably, can be applicable to the industrial production of synthesizing small crystal grain ZSM-5-5 molecular sieve.
Description
Technical field
The present invention is specifically related to a kind of synthetic method of ZSM-5 molecular sieve with small crystal grains.
Background technology
Micro-pore zeolite molecular sieve is a kind of inorganic containing silicon crystal, and its skeleton has containing regular and that ordered arrangement is close with molecular dimension duct, is widely used in fields such as catalysis, ion-exchange and separation.But synthesis of molecular sieve, particularly specific molecular sieve need adopt the template be harmful to human health or safety.Therefore new eco-friendly Zeolite synthesis technique has become one of the most urgent task of catalyzer worker.
ZSM-5 zeolite forms pore canal system by 10 rings, has 3 D pore canal.At the beginning of the seventies in last century, disclose the synthetic method of ZSM-5 molecular sieve, after this, because ZSM-5 molecular sieve is widely used in alkylation, isomerization, disproportionation, selective cracking process and by the reaction such as methanol synthesized gasoline.
And catalyzed reaction requires that zeolite crystal is little, the active centre needed for catalyzed reaction that molecular sieve surface exposes is just many, and catalyst activity is high, and therefore for great majority reaction, less zeolite crystal, catalyzed reaction efficiency is higher.
In ZL89108240.9, have employed the method preparing molecular sieve with Vapor-phase transport method.First a certain amount of Tai-Ace S 150, water glass, sodium hydroxide and deionized water are mixed rear filtration, washing in sequence, obtain amorphous gel.With quadrol (EDA), triethylamine (Et
3a) and the mixed solution of water as template, under 453 ~ 473K react 5 ~ 7d, prepare ZSM-5 molecular sieve powder.It is owing to being that gel component does not have through super-dry, and water is not easy to remove, and adopts a large amount of water and organic amine template, cannot avoid a large amount of organic amine environmental pollution and health problem in building-up process with the technique of synthesis aftertreatment.But the zeolite crystal of the method synthesis is larger.
In WO2005026050, after have employed silicon source and aluminium source and other crystallization raw material plastic, then carry out Silanization reaction, then adopt hydrothermal crystallization method to carry out crystallization again and obtain ZSM-5 molecular sieve with small crystal grains.The method have employed silylating reagent in preparation process, and process is complicated, and with potential safety hazard, and silanization process equalization is more difficult.In USP20060111234, water heat transfer small crystal grain molecular sieve under employing special parameter.Then comparatively high temps and then synthesis of molecular sieve at a lower temperature is first risen in building-up process.In foregoing invention, adopt a large amount of water and organic amine template, a large amount of organic amine environmental pollution and health problem cannot be avoided in building-up process with the technique of synthesis aftertreatment.
In CN101428818A, aluminium source, silicon source, sodium hydroxide and organic amine Isopropylamine plastic are obtained mixture, carries out crystallization and obtain small crystal grain molecular sieve.In foregoing invention, adopt a large amount of water and organic amine template, a large amount of organic amine environmental pollution and health problem cannot be avoided in building-up process with the technique of synthesis aftertreatment.
Summary of the invention
Technical problem to be solved by this invention is the excessive problem of the ZSM-5 molecular sieve crystal grain of vapor-phase synthesis in prior art, provides a kind of synthetic method of new ZSM-5 molecular sieve with small crystal grains, adopts the ZSM-5 molecular sieve of the method synthesis to have the little advantage of crystal grain.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthetic method of ZSM-5 molecular sieve with small crystal grains, comprises the following steps:
A) silicon source, aluminium source and each material of water are mixed, obtain jelly mixture, the mol ratio of each material in mixture is SiO
2: Al
2o
3: H
2o=a: 1: b, wherein the span of a is the span of 12 ~ 350, b is 30 ~ 40000; Basic cpd and acid regulate the pH value of mixture to be 8 ~ 14;
B) said mixture is 0.001 ~ 1.00kgf in vacuum tightness, and temperature is vacuum-drying under 50 ~ 200 DEG C of conditions, obtains dry glue I;
C), after dry glue I being contacted infiltration with template I, dry glue II is obtained;
D) dry glue II is placed in the top in crystallizing kettle, at least one in the moisture or template II in the bottom in crystallizing kettle, at 100 ~ 250 DEG C, crystallization 2 ~ 150 hours, obtains ZSM-5 molecular sieve with small crystal grains;
Wherein, described template I and template II is at least one in TPAOH, 4-propyl bromide, Tri-n-Propylamine, hexahydroaniline; Described heteroatoms metal is at least one in Fe, V, Ge, Co, Ni; With mass ratio range, template I and template II gross weight: contained SiO in dry glue I
2weight=0.001 ~ 5.
In technique scheme, aluminium source preferred version is Tai-Ace S 150, aluminum nitrate, sodium aluminate aluminium salt at least one; Acid preferred version is be selected from least one in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, propionic acid, oxalic acid, amino acid; Alkali preferred version is be selected from least one in sodium oxide, potassium hydroxide, lithium hydroxide, cesium hydroxide; Silicon source preferred version used is be selected from least one in silicon sol, water glass, silica gel; The value preferable range of a is the value preferable range of 12 ~ 200, b is 60 ~ 6000.
When preparing dry glue, with SiO contained by dry glue I
2weighing scale, adds the ZSM-5 crystal seed of 0% ~ 5%.Crystal seed can be the molecular sieve of synthesis, also can be the molecular sieve of the shorter synthesis of crystallization time.After each material mixes, be 0.001 ~ 1.00kgf in vacuum tightness preferable range, temperature preferable range is under 50 ~ 200 DEG C of conditions, and vacuum-drying obtains the dry glue of crystallization synthesis solid.During vacuum-drying, vacuum tightness preferable range is 0.2 ~ 0.9kgf, and temperature preferable range is 80 ~ 160 DEG C, and time of drying, preferable range was 0.1 ~ 50 hour.Synthesis temperature preferable range is 120 ~ 180 DEG C, and crystallization time preferable range is 10 ~ 100 hours.
A small amount of template that the technical program adopts, can airtight middle cooling, crosses Cheng Qian, as direct roasting process organic amine at filtration washing.Add crystal seed, the induction time of crystallization can be reduced, reduce crystallization time.Owing to have employed new dry glue gas-liquid two-phase method synthesis, directly decrease the usage quantity of template on the one hand, cost-saving, two is simple environmental protection, and aftertreatment is more convenient.In the present invention, in molecular sieve process, owing to have employed vacuum drying method, make in drying process, the direct drying method that dry glue is not commonly used, make in the dry glue process of formation, solve alumino silica gel ununiformity in dry glue preferably, make in crystallization process, form little crystal grain.The molecular sieve of the technical program synthesis adopted, grain size 0.05 ~ 2.0 μm, achieves good effect.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the molecular sieve that embodiment 1 is synthesized.
Below by embodiment, the invention will be further elaborated:
Embodiment
[embodiment 1]
By Patent alum 10.0 grams, 20.0 grams, water, 1.0 grams of sulfuric acid dissolution wiring solution-formings.Water glass (containing weight 25% silicon-dioxide, 6.5% sodium hydroxide) 120.0 grams will be taken.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.5 grams.Dry at vacuum tightness 0.5kgf, temperature 90 DEG C, obtain the dry glue of solid.Get dry glue 20.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue top adds 1.5 grams of hexahydroaniline.140 DEG C of airtight lower crystallization 40 hours.Obtain ZSM-5 molecular sieve, XRD characterizes and sees Fig. 1 grain size 0.2 μm.
[embodiment 2]
By Patent alum 5.0 grams, 20.0 grams, water, 0.5 gram of dissolving with hydrochloric acid wiring solution-forming.Water glass (containing concentration 25% silicon-dioxide, 6.5%) 120.0 grams will be taken.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.0 grams.Dry under vacuum tightness 0.2kgf, temperature 50 C, obtain the dry glue of solid.Get dry glue 20.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue top adds 3.0 grams of tetrapropyl amine bromides.130 DEG C of airtight lower crystallization 50 hours.Obtain ZSM-5 molecular sieve, grain size 0.1 μm.
[embodiment 3]
By Patent alum 1.0 grams, 27.0 grams, water, 0.1 gram of sulfuric acid dissolution wiring solution-forming.Water glass (containing concentration 25% silicon-dioxide, 6.5%) 120.0 grams will be taken.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.5 grams.Dry at vacuum tightness 0.8kgf, temperature 80 DEG C, obtain the dry glue of solid.Under add 10.0 grams of water, dry glue adds 5.0 grams of tetrapropyl amine bromides.130 DEG C of airtight lower crystallization 70 hours.Obtain ZSM-5 molecular sieve, grain size 0.08 μm.
[embodiment 4]
Patent alum 5.0 grams, 20.0 grams, water, 0.6 gram of acetic acid and formic acid 0.6g are dissolved wiring solution-forming.Water glass (containing concentration 25% silicon-dioxide, 6.5%) 120.0 grams will be taken.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 0.35 gram.Drying 2 hours at vacuum tightness 0.5kgf, temperature 80 DEG C, rear 150 DEG C of dryings 1 hour, obtain the dry glue of solid.Get dry glue 20.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue top adds 7.0 grams of tetrapropyl amine bromides.100 DEG C of airtight lower crystallization 150 hours.Obtain ZSM-5 molecular sieve, grain size 0.1 ~ 0.2 μm.
[embodiment 5]
Patent alum 15.0 grams, 20.0 grams, water, 1.2 grams of phosphoric acid are dissolved wiring solution-forming.Water glass (containing concentration 25% silicon-dioxide, 6.5%) 120.0 grams will be taken.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 0.1 gram.Drying 49.5 hours under vacuum tightness 0.1kgf, temperature 50 C, rear 200 DEG C of dryings obtain the dry glue of solid for 0.5 hour.Get dry glue 15.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue top adds 10.0 grams of tetrapropyl amine bromides.140 DEG C of airtight lower crystallization 150 hours.Obtain ZSM-5 molecular sieve, grain size 0.05 ~ 0.15 μm.
[embodiment 6]
Patent alum 29.0 grams, 20.0 grams, water, 0.2 gram of propionic acid and 0.5g glycine are dissolved wiring solution-forming.Water glass (containing weight concentration 25% silicon-dioxide, 6.5%) 120.0 grams will be taken.By plastic under above-mentioned two kinds of solution strong mixings.Drying 1 hour at vacuum tightness 1.0kgf, temperature 90 DEG C, rear 120 DEG C of dryings 6 hours, obtain the dry glue of solid.Get dry glue 10.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue adds 5.0 grams of tetrapropyl amine bromides and 3.0g Tri-n-Propylamine.160 DEG C of airtight lower crystallization 150 hours.Obtain ZSM-5 molecular sieve, grain size 0.15 μm.
[embodiment 7]
2.0 grams, aluminium hydroxide, 20.0 grams, water, 4.5 grams of oxalic acids are dissolved wiring solution-forming.To take silicon sol (containing weight concentration 40% silicon-dioxide) 75.0 grams, lithium hydroxide 6.5 grams, water 500.0g is dissolved into solution.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.75 grams.Under vacuum tightness 0.1kgf, temperature 60 C, drying 50 hours, obtains the dry glue of solid.Get dry glue 35.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue adds 3.0 grams of TPAOH and 4.0g tetrapropyl amine bromide.140 DEG C of airtight lower crystallization 100 hours.Obtain ZSM-5 molecular sieve, grain size 0.15 μm.
[embodiment 8]
By nine water aluminum nitrate 20.0 grams, 20.0 grams, water, 1.0 gram of 98% concentrated sulfuric acid dissolution wiring solution-forming.35.0 grams, silica gel will be taken, 5.2 grams, potassium hydroxide.Mix under above-mentioned two kinds of material strong mixings, add crystal seed 0.18 gram.Dry at vacuum tightness 0.001kgf, temperature 90 DEG C, obtain the dry glue of solid.Get dry glue 35.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue adds 10.0 grams of Tri-n-Propylamines.250 DEG C of airtight lower crystallization 2 hours.Obtain ZSM-5 molecular sieve, grain size 0.30 ~ 1.0 μm.
[embodiment 9]
Sodium aluminate 3.0 grams, 20.0 grams, water are dissolved wiring solution-forming.Water glass (containing concentration 25% silicon-dioxide, 6.5%) 120.0 grams will be taken.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.0 grams.Dry at vacuum tightness 0.1kgf, temperature 90 DEG C, obtain the dry glue of solid.Get dry glue 10.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue adds 10.0 grams of tetrapropyl amine bromides.140 DEG C of airtight lower crystallization 150 hours.Obtain ZSM-5 molecular sieve, grain size 1.0 ~ 2.0 μm.
[embodiment 10]
By 4.0 grams, aluminium hydroxide, 20.0 grams, water, 4.5 grams of sulfuric acid dissolution wiring solution-formings.To take silicon sol (containing concentration 40% silicon-dioxide) 75.0 grams, cesium hydroxide 6.5 grams, water 500.0g is dissolved into solution.By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.75 grams.Under vacuum tightness 0.1kgf, temperature 60 C, drying 50 hours, obtains the dry glue of solid.Get dry glue 20.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue adds 10.0 grams of TPAOH.140 DEG C of airtight lower crystallization 100 hours.Obtain ZSM-5 molecular sieve, grain size 0.15 μm.
Claims (1)
1. a synthetic method for ZSM-5 molecular sieve with small crystal grains, comprises the following steps: Patent alum 5.0 grams, 20.0 grams, water, 0.6 gram of acetic acid and formic acid 0.6g are dissolved wiring solution-forming; Water glass 120.0 grams containing 25 % by weight silicon-dioxide and 6.5 % by weight sodium hydroxide will be taken; By plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 0.35 gram; At vacuum tightness 0.5kgf/cm
2, at temperature 80 DEG C dry 2 hours, rear 150 DEG C of dryings 1 hour, obtain the dry glue of solid; Get dry glue 20.0g and put into crystallizing kettle inner upper, under add 10.0 grams of water, dry glue top adds 7.0 grams of tetrapropyl amine bromides; 100 DEG C of airtight lower crystallization 150 hours; Obtain ZSM-5 molecular sieve, grain size 0.1 ~ 0.2 μm.
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| CN104445260A (en) * | 2014-11-18 | 2015-03-25 | 大连龙泰科技发展有限公司 | Small-crystal-grain ZSM-5 molecular sieve, preparation method thereof, and application thereof to preparation of aromatic hydrocarbon by iso-butane |
| CN104724720B (en) * | 2015-03-18 | 2017-08-15 | 宁夏大学 | A kind of synthetic method of the molecular sieves of HZSM 5 |
| CN108059170A (en) * | 2017-12-20 | 2018-05-22 | 广东工业大学 | A kind of controllable method for preparing of the ZSM-5 molecular sieve grown along c-axis |
| CN112408419A (en) * | 2020-12-17 | 2021-02-26 | 河南科技大学 | Preparation method of hierarchical porous ZSM-5 nano zeolite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100228A (en) * | 1988-01-18 | 1988-08-03 | 太原工业大学 | The synthetic method of mordenite in the non-aqueous system |
| CN101538051A (en) * | 2009-05-06 | 2009-09-23 | 北京化工大学 | Method for preparing ZSM-5 zeolite catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100228A (en) * | 1988-01-18 | 1988-08-03 | 太原工业大学 | The synthetic method of mordenite in the non-aqueous system |
| CN101538051A (en) * | 2009-05-06 | 2009-09-23 | 北京化工大学 | Method for preparing ZSM-5 zeolite catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis of zeolites by water-organic vapor-phase transport;Man-Hoe Kim et al.;《Microporous Materials》;19931231;第1卷;第191-200页 * |
| 双模板剂气相转移法合成杂原子磷酸铝分子筛;韶晖等;《石油化工》;20071231;第36卷(第12期);第1205-1209页 * |
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