CN103121690A - Method for synthetizing mordenite by utilizing vapor phase process - Google Patents
Method for synthetizing mordenite by utilizing vapor phase process Download PDFInfo
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- CN103121690A CN103121690A CN2011103699584A CN201110369958A CN103121690A CN 103121690 A CN103121690 A CN 103121690A CN 2011103699584 A CN2011103699584 A CN 2011103699584A CN 201110369958 A CN201110369958 A CN 201110369958A CN 103121690 A CN103121690 A CN 103121690A
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Abstract
The invention relates to a method for synthetizing mordenite by utilizing a vapor phase process, mainly solving the problems that in the prior art, the process is complicated and the environment is polluted when the mordenite is synthetized by the existing vapor phase method. The method provided by the invention comprises the following steps: evenly mixing a silicon source, an aluminum source and water, thereby obtaining a mixture; drying the mixture at the temperature of 50 to 200 DEG C, thereby obtaining a dry glue; putting the dry glue into the upper part of the inside of a crystallization kettle container; and crystallizing at the temperature of 100 to 250 DEG C for 4 to 150 hours, thereby obtaining the mordenite. According to the adopted technical scheme, the problems are solved well. The method provided by the invention can be applied to the industrial production of the mordenite.
Description
Technical field
The present invention relates to a kind of method of vapor phase process synthesizing flokite.
Background technology
Mordenite molecular sieve is a kind of inorganic silicon crystal that contains, and its skeleton has and contains rule and ordered arrangement and molecular dimension close duct, is widely used in fields such as catalysis, ion-exchange and separation.Be widely used in the sorbent material of divided gas flow or liquid mixture.This zeolite has good acidity simultaneously, also is usually used in the catalytic reaction processes such as catalytic cracking, alkylation, isomerization, disproportionation and transalkylation, reformation.Therefore mordenite is inorganic materials commonly used.
Mordenite has octatomic ring and twelve-ring and mutually intersects the molecular sieve of microvoid structure.The synthetic method of traditional mordenite molecular sieve is under the alkaline aqueous solution condition, and the compound that contains aluminium and silicon is synthetic under hydrothermal condition.Because molecular sieve is widely used industrial, although the means of synthetic method and modification are also constantly progressive, but the continuous expansion along with the molecular sieve application, the industrial scale of molecular sieve is increasing, synthesis of molecular sieve, particularly specific molecular sieve need adopt the template that the human health or safety is harmful to, and building-up process is because the higher production capacity of water-content is limited, the difficult problem such as mother liquor difficult treatment after molecular sieve filtration.Therefore the new eco-friendly technique of Zeolite synthesis cheaply is developing direction.
In USP4585640,5219576, adopted silicon source, aluminium source and other synthesis material to carry out plastic, and added organic amine in the synthetic liquid of reaction.First water is mixed with the silicon source, then be combined with it with water, organism and mineralizer mixture and be prepared into sizing material in another kind of aluminium source.Carry out the crystallization filtration washing after plastic and obtain mordenite, then roasting, exchange.The rear molecular sieve of exchange carries out roasting again and obtains hydrogen type molecular sieve.Adopted organic amine in building-up process, synthetic rear mother liquor processing cost is higher.It can't avoid a large amount of organic amine environmental pollutions and health problem owing to adopting a large amount of water and organic amine template in building-up process in the technique of building-up process and synthetic aftertreatment.
In CN1230518, adopted take water glass, mineral acid, inorganic salt and aluminium salt or aluminate as raw material and synthesized, synthetic water/aluminum oxide is than 200～1000, complete crystallization and make mordenite by filtration, washing, drying, and also add anion surfactant (Sodium dodecylbenzene sulfonate) in building-up process.In CN1328961, adopted the technical scheme of the organic amine template such as hexamethylene imine to come the synthesizing flokite molecular sieve.In this invention, after being mixed, silicon source, aluminium source, alkali, template and water add again template to carry out the crystallization synthesis of molecular sieve.Its water/silicon oxide is than 10～200.Adopted specific organic amine to shorten crystallization time in building-up process, synthetic rear mother liquor processing cost is higher.It also can't avoid a large amount of organic amine environmental pollutions and health problem owing to adopting a large amount of water and organic amine template in building-up process in the technique of building-up process and synthetic aftertreatment.
In CN1463921, adopted take the silicon source, mineral acid, organism and aluminium source prepare burden in sequence as raw material, at a certain temperature the crystallization synthesis of molecular sieve.Filter, wash after synthetic.Wherein adding hexanolactam in synthetic liquid is organic directed agents.It also can't avoid a large amount of organic amine environmental pollutions and health problem owing to adopting a large amount of water and organic amine template in building-up process in the technique of building-up process and synthetic aftertreatment.
Summary of the invention
Complicated, the problem that environmental hazard is arranged of preparation process when technical problem to be solved by this invention is the gas phase synthesizing flokite provides a kind of method of new vapor phase process synthesizing flokite, and the method has advantages of that building-up process is simple, environmental protection.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of vapor phase process synthesizing flokite comprises the following steps:
A) each material of silicon source, aluminium source and water is mixed, obtain colloidal mixture, in mixture, the mol ratio of each material is SiO
2: Al
2O
3: H
2O=a: 1: b, wherein the span of a is that the span of 1～100, b is 5～6000; The pH value of regulating mixture with basic cpd and acid is 8～14;
B) mixture is dry under 50～200 ℃ of conditions in temperature, obtains dried glue I;
C) dried glue I is contacted with template I infiltrate after, obtain dried glue II;
D) dried glue II is placed in top in crystallizing kettle, at least a in the moisture or template II in the bottom in crystallizing kettle 100～250 ℃ of lower crystallization 4～150 hours, obtains mordenite;
Wherein, template is at least a in tetraethyl ammonium hydroxide, tetraethylammonium bromide, n-Butyl Amine 99, triethylamine, quadrol, ammoniacal liquor; In weight ratio, template I and template II gross weight: contained SiO in dried glue I
2Weight=0.001～5.
In technique scheme, will contain the acidity that aluminium salt is dissolved in the water and uses acid or alkali regulator solution, and add or do not add as sodium chloride salt etc.Alkalescence with dissolvings such as sodium hydroxide, is regulated with alkali such as sodium hydroxide in the silicon such as silicon sol or water glass source.With above-mentioned two kinds of solution plastics, obtain the sial colloid.Adopt fully in the plastic process and stir as good.The aluminium source can be Tai-Ace S 150, aluminum nitrate, sodium aluminate aluminium salt one or more, dissolve in water, can be also the dissolving of sodium hydroxide highly basic.Silicon used source preferred version is at least a in silicon sol, water glass, silica gel, can be also the dissolving of sodium hydroxide highly basic.Preferred technical scheme is with the silicon contained SiO in source
2Weighing scale also adds 0.5～5% mordenite crystal seed when being to prepare dried glue, crystal seed can be the molecular sieve that synthesizes, and can be also the shorter synthetic molecular sieve of crystallization time.
Above-mentioned sial colloid at 70～100 ℃ of lower evaporative removal water, is obtained dried glue, also can be dry more than under 100 ℃, 0.5～150 hour time.Obtain the synthetic dried glue of required solid of crystallization.Also dried glue can be put into the top of crystallizing kettle, then add a small amount of water or and template.Airtight crystallization at a certain temperature 4～150 hours.Taking-up obtains the crystallization product.
The present invention can obtain mercerising molecular sieve sial molecule mol ratio can be greater than 50.Sodium type molecular sieve obtained above can first roasting after or directly carry out ion-exchange, for the preparation of non-sodium type mordenite molecular sieve.
Owing to having adopted new dried glue gas-liquid two-phase method synthetic, directly reduced on the one hand the usage quantity of template; In the mordenite glue preparation process of routine, have template to exist simultaneously always, solve the environmental issue of template, and present method is not used template in the dried glue of preparation; A small amount of template that the technical program adopts can airtight middle cooling, and then a small amount of organic amine adopts the easy to handle method, processes as direct roasting, and preparation process is simple like this, and environmental protection has obtained technique effect preferably.
Description of drawings
Fig. 1 is the SEM collection of illustrative plates of the synthetic molecular sieve of embodiment 1.
The invention will be further elaborated below by embodiment:
Embodiment
[embodiment 1]
With Patent alum 12.0 grams, water 30.0 gram dissolving wiring solution-formings.To take water glass (containing weight concentration 21% silicon-dioxide, sodium oxide 6.5%) 120.0 grams.With plastic under above-mentioned two kinds of solution strong mixings, stir after 2 hours, drying is 7 hours under 90 ℃, obtains the dried glue of solid.Get the dried glue of 10.0g, put into airtight crystallizing kettle internal upper part, dried glue top added 6.0 gram tetraethyl-amine bromides, and 20.0 gram water are put in the bottom in crystallizing kettle, 150 ℃ of lower crystallization 30 hours.Obtain mordenite molecular sieve, the SEM of its molecular sieve characterizes and sees Fig. 1.
[embodiment 2]
With Patent alum 26.0 grams, 10g sodium-chlor, water 30 grams, oxalic acid 1g and propionic acid 1.0g dissolving wiring solution-forming.To take water glass (containing concentration 21% silicon-dioxide, sodium oxide 6.5%) 120.0 grams.With plastic under above-mentioned two kinds of solution strong mixings, after, drying is 6 hours under 90 ℃, obtains the dried glue of solid.Get the dried glue of 10.0g, put into airtight crystallizing kettle internal upper part, the bottom in crystallizing kettle adds 20.0 gram water and 6.0 gram ammoniacal liquor.170 ℃ of airtight lower crystallization 45 hours.Obtain mordenite molecular sieve.
[embodiment 3]
Patent alum 2.8 grams, water 100.0 grams are added acetic acid 0.5g and formic acid 3g dissolving wiring solution-forming.To take water glass (containing weight concentration 21% silicon-dioxide, sodium oxide 6.5%) 120.0 grams, water 318.0 grams.Under above-mentioned two kinds of solution strong mixings, add crystal seed 1.0 grams, stir after 2 hours, under 90 ℃ dry 20 hours, under 200 ℃ dry 2 hours, obtain the dried glue of solid.Get the dried glue of 10.0g and put into airtight crystallizing kettle internal upper part, the 6.0 gram tetraethyl ammonium hydroxide aqueous solution (25% weight percentage) are put on dried glue top, and the bottom in crystallizing kettle adds 20.0 gram water.150 ℃ of airtight lower crystallization 60 hours.Obtain mordenite molecular sieve.
[embodiment 4]
With Patent alum 270.0 grams, water 1200 grams, concentrated hydrochloric acid 6.2g and 2.0g glycine dissolving wiring solution-forming.To take water glass (containing concentration 21% silicon-dioxide, sodium oxide 6.5%) 120.0 grams, water 600 grams.With plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 0.3 gram, stir after 3 hours, drying is 30 hours under 90 ℃, obtains the dried glue of solid.Get the dried glue of 10g and put into airtight crystallizing kettle internal upper part,, the bottom in crystallizing kettle adds 20.0 gram diethylamine aqueous solutions, contains diethylamine 6.0g.100 ℃ of airtight lower crystallization 150 hours.Obtain mordenite molecular sieve.
[embodiment 5]
With sodium aluminate 2.0 grams, water 80.0 gram dissolving wiring solution-formings.To take water glass (containing weight concentration 21% silicon-dioxide, sodium oxide 6.5%) 120.0 grams.With plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.25 grams, stir after 2 hours, under 90 ℃ dry 1 hour, then under 170 ℃ dry 30 hours, obtain the dried glue of solid.Get the dried glue of 10.0g and put into airtight crystallizing kettle internal upper part, 6.0 gram tetraethyl ammonium hydroxides are put on dried glue top, and the bottom in crystallizing kettle adds 6.0 gram water.250 ℃ of airtight lower crystallization 4 hours.Obtain mordenite molecular sieve.
[embodiment 6]
With aluminium hydroxide 20.0 grams.To take silica gel 40.0 grams, sodium hydroxide 8.0 grams, water 23.0 grams mixing.With above-mentioned two kinds of material strong mixings 2 hours, add crystal seed 1.0 grams, stir after 2 hours, drying is 50 hours under 50 ℃, obtains the dried glue of solid.Get the dried glue of 10.0g and put into airtight crystallizing kettle internal upper part, 6.0 gram tetraethylammonium bromides are put on dried glue top, and the bottom in crystallizing kettle adds 40 gram ethylamine solutions, contains ethamine 2.0g.180 ℃ of airtight lower crystallization 20 hours.Obtain mordenite molecular sieve.
[embodiment 7]
With aluminum nitrate 5.2 grams, sulfuric acid (concentration 98%) 1.0 grams, water 20.0 gram dissolving wiring solution-formings.To take silicon sol (containing weight concentration 40.0% silicon-dioxide) 100 grams, potassium hydroxide 5.5 grams and lithium hydroxide 2.0g, water 100.0 grams, be dissolved into solution.With plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 2.0 grams, stir after 2 hours and to filter, 160 ℃ of dryings 0.1 hour obtain the dried glue of solid.Get the dried glue of 10.0g and put into airtight crystallizing kettle internal upper part, 6.0 gram triethylamines are put on dried glue top, and the bottom in crystallizing kettle adds 20.0 gram water.120 ℃ of airtight lower crystallization 100 hours.Obtain mordenite molecular sieve.
[embodiment 8]
With aluminum nitrate 5.2 grams, sulfuric acid (concentration 98%) 1.0 grams, water 50.0 gram dissolving wiring solution-formings.To take silica gel 40.0 grams, cesium hydroxide 5.5 grams, water 100.0 grams, be dissolved into solution.With plastic under above-mentioned two kinds of solution strong mixings, add crystal seed 1.0 grams, stir after 2 hours and filter.Dry under 90 ℃, obtain the dried glue of solid.Get the dried glue of 10.0g and put into airtight crystallizing kettle internal upper part, 6.0 gram tetraethyl ammonium hydroxides are put on dried glue top, and the bottom in crystallizing kettle adds 6.0 gram water.190 ℃ of airtight lower crystallization 20 hours.Obtain mordenite molecular sieve.
[embodiment 9]
With Patent alum 80.0 grams, water 600.0 grams, phosphatase 11 .0g and propionic acid 1.0g dissolving wiring solution-forming.To take water glass (containing concentration 21.0% silicon-dioxide, sodium oxide 6.5%) 120.0 grams.After plastic under above-mentioned two kinds of solution strong mixings, drying is 10 hours under 90 ℃, obtains the dried glue of solid.Get the dried glue of 10.0g, put into airtight crystallizing kettle internal upper part, 2.0g tetrapropyl amine bromide is put on dried glue top, and the bottom in crystallizing kettle adds 20.0 gram water and 6.0 gram ammoniacal liquor.170 ℃ of airtight lower crystallization 30 hours.Obtain mordenite molecular sieve.
Claims (6)
1. the method for a vapor phase process synthesizing flokite comprises the following steps:
A) each material of silicon source, aluminium source and water is mixed, obtain colloidal mixture, in mixture, the mol ratio of each material is SiO
2: Al
2O
3: H
2O=a: 1: b, wherein the span of a is that the span of 1～100, b is 5～6000; The pH value of regulating mixture with basic cpd and acid is 8～14;
B) mixture is dry under 50～200 ℃ of conditions in temperature, obtains dried glue I;
C) dried glue I is contacted with template I infiltrate after, obtain dried glue II;
D) dried glue II is placed in top in crystallizing kettle, at least a in the moisture or template II in the bottom in crystallizing kettle 100～250 ℃ of lower crystallization 4～150 hours, obtains mordenite;
Wherein, template is at least a in tetraethyl ammonium hydroxide, tetraethylammonium bromide, n-Butyl Amine 99, triethylamine, quadrol, ammoniacal liquor; In weight ratio, template I and template II gross weight: contained SiO in dried glue I
2Weight=0.001～5.
2. the method for vapor phase process synthesizing flokite according to claim 1 is characterized in that silicon used source is at least a in silicon sol, water glass, silica gel; The aluminium source is at least a in Tai-Ace S 150, aluminum nitrate, aluminium hydroxide, sodium aluminate; Alkali is be selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide at least a; Acid used is selected from least a in sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid, propionic acid, oxalic acid, amino acid.
3. the method for vapor phase process synthesizing flokite according to claim 1, the span that it is characterized in that the optimization of described a is that the span of 2～60, b is 10～600.
4. the method for vapor phase process synthesizing flokite according to claim 1, is characterized in that, with the contained SiO of dried glue I
2Weighing scale, preparation adds 0.1%～5% mordenite crystal seed during dried glue.
5. the method for vapor phase process synthesizing flokite according to claim 1, is characterized in that b) the mixture drying temperature is 80～160 ℃ in step, 0.1～50 hour time of drying.
6. Zeolite synthesis method according to claim 1, is characterized in that d) be 120～180 ℃ of lower crystallization 10～100 hours at synthesis temperature in step.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892242A (en) * | 2021-01-29 | 2021-06-04 | 江西师范大学 | High-flux mordenite molecular sieve membrane and preparation method and application thereof |
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|---|---|---|---|---|
| CN1051334A (en) * | 1989-10-28 | 1991-05-15 | 太原工业大学 | The method of synthesis of zeolite by vapor phase |
| CN1490245A (en) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | High silicon mordenite and preparing method thereof |
| CN1648046A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Processfor preparing mordenite and beta zeolite mixed crystal material |
| CN101384365A (en) * | 2006-02-14 | 2009-03-11 | 埃克森美孚化学专利公司 | Method of preparing a molecular sieve composition |
-
2011
- 2011-11-18 CN CN201110369958.4A patent/CN103121690B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051334A (en) * | 1989-10-28 | 1991-05-15 | 太原工业大学 | The method of synthesis of zeolite by vapor phase |
| CN1490245A (en) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | High silicon mordenite and preparing method thereof |
| CN1648046A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Processfor preparing mordenite and beta zeolite mixed crystal material |
| CN101384365A (en) * | 2006-02-14 | 2009-03-11 | 埃克森美孚化学专利公司 | Method of preparing a molecular sieve composition |
Non-Patent Citations (1)
| Title |
|---|
| 周荣飞等: "丝光沸石分子筛膜的制备与表征", 《江西师范大学学报(自然科学版)》, vol. 33, no. 4, 31 August 2009 (2009-08-31), pages 419 - 422 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112892242A (en) * | 2021-01-29 | 2021-06-04 | 江西师范大学 | High-flux mordenite molecular sieve membrane and preparation method and application thereof |
| CN112892242B (en) * | 2021-01-29 | 2022-08-02 | 江西师范大学 | High-flux mordenite molecular sieve membrane and preparation method and application thereof |
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