CN102225773A - Preparation method of molecular sieve - Google Patents
Preparation method of molecular sieve Download PDFInfo
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- CN102225773A CN102225773A CN 201110066897 CN201110066897A CN102225773A CN 102225773 A CN102225773 A CN 102225773A CN 201110066897 CN201110066897 CN 201110066897 CN 201110066897 A CN201110066897 A CN 201110066897A CN 102225773 A CN102225773 A CN 102225773A
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- molecular sieve
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- sodium hydroxide
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Abstract
The invention relates to a preparation method of a molecular sieve. The preparation method comprises the following steps of: mixing a template agent, an aluminum source, a silicon source, sodium hydroxide and water and uniformly stirring to obtain a mixture I; placing the mixture I in a sealed reaction kettle and aging to obtain an EUO-type directing agent; mixing the aluminum source, the silicon source, sodium hydroxide and water, uniformly stirring to obtain a colloid mixture II, and uniformly mixing the colloid mixture II with the EUO-type directing agent to obtain a mixture III; or uniformly mixing the aluminum source, the silicon source, sodium hydroxide and water with the EUO-type directing agent to obtain the mixture III, placing the mixture III in a sealed reaction kettle, crystallizing and filtering, washing and drying to obtain EUO-type molecular sieve powder. The preparation method provided by the invention has the advantages of lowering consumption of the template agent and saving the production cost.
Description
Technical field
The invention belongs to a kind of preparation method of molecular sieve.
Background technology
People such as John L.CasCi have issued the molecular sieve with EUO structure first in European patent Eur.Pat.Appl.42226 (USP4537754) in 1981, because its unique pore passage structure, at xylene isomerization (USP 20010051757), C
8Have excellent catalytic performance in the aromatics isomerization reactions such as (CN1260239A), therefore have good commercial and be worth and application prospect.The preparation process of this molecular sieve is to prepare a kind of aqueous mixture earlier, and this mixture contains at least a quadrivalent element oxide compound YO
2, at least a trivalent element oxide compound X
2O
3Alkyl derivative with the following polymethylene α-ω diamines of at least a structural formula:
This alkyl derivative is the template of synthetic EUO type structure molecular screen.Wherein n gets 3-12, R
1-R
6Can get identical or different hydro carbons or hydroxyl hydro carbons group, contain 1-8 carbon atom, 5 R can be arranged at the most
1-R
6Group can be hydroxyl.
Lin Min etc. (CN 1796278A) have reported with fluorochemical as mineralizer, the two ammoniums of dihydroxy-hexane are template, tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters are the silicon source, aluminum isopropylate or isobutanol aluminum are the aluminium source, earlier through catching up with alcohol to make gel mixture, 120 ℃～220 ℃ following crystallization 1～30 day, obtain the method for EUO structure molecular screen.
The EUO structural zeolite of in European patent application EP-A-0042226, describing, be to adopt expensive aerosil, use the degraded product or the described derivative precursor of polymethylene α-ω two ammonium alkyl derivatives or described derivative to be prepared from as template.
CN 1327946A is in the presence of by diphenyl-methyl Dimethyl Ammonium (DBDMA) or their the precursor-derived organic structuring agent that obtains, with synthetic EUO structure molecular screen in the presence of zeolite structured identical zeolitic material crystal seed at least a and to be synthesized.Wherein template and the material of oxide compound are than (Q/YO
2) the optimal proportion scope be 0.01-1.
CN1260239A discloses a kind of preparation method of EUO structure Si-Al molecular sieve, it is characterized in that this method is hydrolysis in the aqueous solution of template R with aluminium source and silicon source, catch up with alcohol at 30-100 ℃, add fluorochemical, obtain mole proportioning and be (0.05-0.7) Q: (0.01-0.2) Al
2O
3: SiO
2: (0.4-2) F
-: (2-100) H
2O.Wherein template Q is the dihydroxy-hexane diamine, and template is 0.05-0.7 with the optimal proportion scope of the material ratio of oxide compound.
Aforesaid method all is directly to add a certain amount of organic formwork agent and Q/YO
2Scope is mostly between 0.01-1.Used template is organism mostly, and prices are rather stiff, under industrialized promotion, reduces the usage quantity of template or replaces organic formwork will become total trend of research work with low-cost template.
Summary of the invention
The purpose of this invention is to provide a kind of usage quantity that reduces template, thus the preparation method of the EUO type molecular sieve that saves production cost.
The method of the EUO of preparation molecular sieve provided by the invention comprises the steps:
(1) your ratio of template, aluminium source, silicon source, sodium hydroxide and hydromassage is template: Al
2O
3: SiO
2: Na
2O: H
2O=(0.5-40): 1: (30-300): (1.2-26): (300-2500) mix, and stir, obtain the mixture I;
(2) the mixture I is placed closed reaction kettle at 100 ℃～200 ℃, under preferred 120 ℃-180 ℃ temperature ageing 5-48 hour, preferred 5-27 hour, obtain EUO type directed agents;
(3) A: your ratio of aluminium source, silicon source, sodium hydroxide and hydromassage is Al
2O
3: SiO
2: Na
2O: H
2O=1: (30-800): (1.2-65): (25-3000) mix, and stir the colloid admixture II that obtains, the per-cent that accounts for the reactant cumulative volume by EUO type directed agents is 5%-80%, preferred 10-40% mixes EUO type directed agents and mixture II, obtains the mixture III;
Or B: be Al in molar ratio
2O
3: SiO
2: Na
2O: H
2O=1: (30-800): (1.2-65): (25-3000), aluminium source, silicon source, sodium hydroxide, water and EUO type directed agents are mixed, obtain the mixture III, wherein to account for the per-cent of reactant cumulative volume be 5%-80% to EUO type directed agents, preferred 10-40%; (4) the mixture III is placed closed reactor crystallization 1～10 day under 140 ℃～200 ℃ temperature, more after filtration, washing, under 100-120 ℃ of condition dry 2-8 hour, promptly get EUO type molecular screen primary powder.
Aforesaid silicon source can be selected liquid-state silicon colloidal sol, white carbon black, silica gel or silicon aluminium microsphere for use; The aluminium source is selected sodium metaaluminate, silicon aluminium microsphere, the rich diaspore of plan or aluminium hydroxide, preferred sodium metaaluminate for use.Template can be selected C6, pentamethonium or phenylbenzene Dimethyl Ammonium for use, preferred C6.
The mol ratio of template, aluminium source, silicon source, sodium hydroxide and water is preferably template in the step (1): Al
2O
3: SiO
2: Na
2O: H
2O=(4-22): 1: (30-200): (4.2-20.5): (500-1500).
Aluminium source, silicon source, sodium hydroxide and water mol ratio are preferably Al in the step (3)
2O
3: SiO
2: Na
2O: H
2O=1: (30-280): (2.8-25): (500-2250).
The present invention compared with prior art has following advantage:
1, key is to have introduced the use that directed agents replaces organic formwork agent in the preparation process of EUO structure Si-Al molecular sieve, has synthesized the EUO type molecular sieve with higher crystallinity, has reduced production cost, has certain industrial application value.
2, adopt that synthetic EUO type zeolite product of the present invention stable performance, degree of crystallinity height, silica alumina ratio scope are big, heat and hydrothermal stability height.
Embodiment
Embodiment 1
A. liquid-state silicon colloidal sol 6.69ml, 0.42g sodium hydroxide and the 10.2ml water with 1.45g template C6,0.2g sodium metaaluminate, 5.98mol/L mixes, and stirring obtains the mixture I, goes into still, in 180 ℃ of about 5h of ageing, makes directed agents.
B. with the sodium hydroxide of 0.2g sodium metaaluminate, 0.38g, liquid-state silicon colloidal sol and the 10ml water of 8.24ml 5.98mol/L, the colloid admixture II that stirs and obtain.Get the EUO type directed agents 3.97ml and the mixture II that prepare in the above-mentioned a step and mix, place closed reactor crystallization 6 days under 180 ℃ of conditions, more after filtration, washing, under 110 ℃ of conditions dry 6 hours, promptly get EUO type molecular screen primary powder.
Embodiment 2
A. liquid-state silicon colloidal sol 13.4ml, 0.61g sodium hydroxide and the 19.5ml water with 3g template C6,0.2g sodium metaaluminate, 5.98mol/L mixes, and stirring obtains the mixture I, goes into still, in 180 ℃ of about 17h of ageing, makes directed agents.
B. the colloid admixture II that the water of the liquid-state silicon colloidal sol of 0.2g sodium metaaluminate, 0.4g sodium hydroxide, 10.70ml5.98mol/L and 6ml is stirred and obtains.Get the EUO type directed agents 5.29ml and the mixture II that prepare in the above-mentioned a step and mix, place closed reactor crystallization 5 days under 185 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry 2 hours molecular screen primary powder.
Embodiment 3
A. liquid-state silicon colloidal sol 21.5ml, 0.80g sodium hydroxide and the 27ml water with 4.34g template C6,0.2g sodium metaaluminate, 5.98mol/L mixes, and stirring obtains the mixture I, goes into still, in 180 ℃ of about 27h of ageing, makes directed agents.
B. with the sodium hydroxide of 0.2g sodium metaaluminate, 3ml 2.25mol/L, the liquid-state silicon colloidal sol of 8.24ml 5.98mol/L and the colloid admixture II that 4ml water stirs and obtains.Get the EUO type directed agents 6.50ml and the mixture II that prepare in the above-mentioned a step and mix, place closed reactor crystallization 2 days under 180 ℃ of conditions, more after filtration, washing, under 110 ℃ of conditions dry 2 hours, molecular screen primary powder.
Embodiment 4
A. 1.45g template C6,1.13g silicon aluminium microsphere, 3.87g white carbon black, 0.42g sodium hydroxide and 10.2ml water are mixed, stirring obtains the mixture I, goes into still, in 180 ℃ of about 15h of ageing, makes directed agents.
B. the EUO type directed agents 6.86ml for preparing in 3.87g white carbon black, 1.13g silicon aluminium microsphere, 0.72g sodium hydroxide, 11ml water and the above-mentioned a step is mixed, place closed reactor crystallization under 180 ℃ of conditions to take out after 3 days, quenching is to room temperature, wash with water to neutrality, obtain white powder in dry 8 hours down in 120 ℃ behind the suction filtration, be EUO type molecular screen primary powder.
Embodiment 5
A. 3g template C6,0.13g aluminium hydroxide, 8.69g white carbon black, 0.61g sodium hydroxide and 19.5ml water mixing and stirring are obtained the mixture I, go into still,, make directed agents in 180 ℃ of about 20h of ageing.
B. the EUO type directed agents 10ml for preparing in 4.64g macroporous silica gel, 0.36g silicon aluminium microsphere, 0.77g sodium hydroxide, 12ml water and the above-mentioned a step is mixed, place closed reactor to take out in 3 days 160 ℃ of reactions, quenching is to room temperature, wash with water to neutrality, after 100 ℃ of following dryings, obtain white powder behind the suction filtration, be EUO type molecular screen primary powder.
Embodiment 6
A. 4.34g phenylbenzene Dimethyl Ammonium, 0.56g silicon aluminium microsphere, 10.5g white carbon black, 0.80g sodium hydroxide and 27ml water mixing and stirring are obtained the mixture I, go into still,, make directed agents in 150 ℃ of about 24h of ageing.
B. the EUO type directed agents 5.29ml for preparing in liquid-state silicon colloidal sol, 0.38g sodium hydroxide and the 10ml water of 0.2g sodium metaaluminate, 10.70ml 5.98mol/L and the above-mentioned a step is mixed, place closed reactor under 175 ℃ of conditions, to leave standstill crystallization 4 days, again after filtration, washing, under 100 ℃ of conditions dry 2 hours.
Embodiment 7
A. earlier 1.5g template pentamethonium, 3.5g white carbon black, 2.0g silicon aluminium microsphere, 0.77g sodium hydroxide and 11ml water mixing and stirring are obtained the mixture I, go into still,, promptly get directed agents in 150 ℃ of about 20h of ageing.
B. the colloid admixture II that 4.8g white carbon black, 1.13g silicon aluminium microsphere, 0.72g sodium hydroxide and 8.5ml water are stirred and obtains.Getting the EUO type directed agents 3ml and the mixture II that prepare in the above-mentioned a step mixes, place closed reactor to leave standstill crystallization under 185 ℃ of conditions and take out after 3 days, quenching washes with water to neutrality to room temperature, after 100 ℃ of following dryings, obtain white powder behind the suction filtration, be EUO type molecular sieve.
Embodiment 8
A. 2.0g template pentamethonium, 4.5g white carbon black, 1.0g silicon aluminium microsphere, 0.76g sodium hydroxide and 11ml water mixing and stirring are obtained the mixture I, go into still,, promptly get directed agents in 150 ℃ of about 20h of ageing.
B. the colloid admixture II that 4.85g macroporous silica gel, 1.13g silicon aluminium microsphere, 0.71g sodium hydroxide and 13.5ml water are stirred and obtains.Getting the EUO type directed agents 4ml and the mixture II that prepare in the above-mentioned a step mixes, place closed reactor to leave standstill crystallization under 170 ℃ of conditions and take out after 3 days, quenching washes with water to neutrality to room temperature, after 100 ℃ of following dryings, obtain white powder behind the suction filtration, be EUO type molecular sieve.
Embodiment 9
A. 3.5g template pentamethonium, 4.5g white carbon black, 2.0g are intended rich diaspore, 0.95g sodium hydroxide and 11ml water mixing and stirring and obtain the mixture I, go into still,, promptly get directed agents in 150 ℃ of about 27h of ageing.
B. the EUO type directed agents 3.5ml for preparing in 2.88g white carbon black, 1.13g silicon aluminium microsphere, 0.8g sodium hydroxide and 10ml water and the above-mentioned a step is mixed, placing closed reactor to leave standstill crystallization under 185 ℃ of conditions took out after 4 days, quenching is to room temperature, wash with water to neutrality, after 100 ℃ of following dryings, obtain white powder behind the suction filtration, be EUO type molecular sieve.
Claims (11)
1. the preparation method of a molecular sieve is characterized in that comprising the steps:
(1) your ratio of template, aluminium source, silicon source, sodium hydroxide and hydromassage is template: Al
2O
3: SiO
2: Na
2O: H
2O=0.5-40: 1: 30-300: 1.2-26: 300-2500 mixes, and stirs, and obtains the mixture I;
(2) the mixture I is placed closed reaction kettle under 100 ℃～200 ℃ temperature ageing 5-48 hour, obtain EUO type directed agents;
(3) A: your ratio of aluminium source, silicon source, sodium hydroxide and hydromassage is Al
2O
3: SiO
2: Na
2O: H
2O=1: 30-800: 1.2-65: 25-3000 mixes, and stirs the colloid admixture II that obtains, the per-cent that accounts for the reactant cumulative volume by EUO type directed agents is 5%-80%, preferred 10-40% mixes EUO type directed agents and mixture II, obtains the mixture III;
Or B: be Al in molar ratio
2O
3: SiO
2: Na
2O: H
2O=1: 30-800: 1.2-65: 25-3000 mixes aluminium source, silicon source, sodium hydroxide, water and EUO type directed agents, obtains the mixture III, and wherein to account for the per-cent of reactant cumulative volume be 5%-80% to EUO type directed agents, preferred 10-40%;
(4) the mixture III is placed closed reactor crystallization 1～10 day under 140 ℃～200 ℃ temperature, more after filtration, washing, under 100-120 ℃ of condition dry 2-8 hour, promptly get EUO type molecular screen primary powder.
2. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that described silicon source is liquid-state silicon colloidal sol, white carbon black, silica gel or silicon aluminium microsphere.
3. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that described aluminium source is sodium metaaluminate, silicon aluminium microsphere, the rich diaspore of plan or aluminium hydroxide.
4. the preparation method of a kind of molecular sieve as claimed in claim 3 is characterized in that described aluminium source is a sodium metaaluminate.
5. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that described template is C6, pentamethonium or phenylbenzene Dimethyl Ammonium.
6. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that described template is a C6.
7. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that the mol ratio of template, aluminium source, silicon source, sodium hydroxide and water in the described step (1) is preferably template: Al
2O
3: SiO
2: Na
2O: H
2O=4-22: 1: 30-200: 4.2-20.5: 500-1500.
8. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that aluminium source, silicon source, sodium hydroxide and water mol ratio are preferably Al in the described step (3)
2O
3: SiO
2: Na
2O: H
2O=1: 30-280: 2.8-25: 500-2250.
9. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that the ageing temperature is 120 ℃-180 ℃ in the described step (2).
10. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that digestion time is 5-27 hour in the described step (2).
11. the preparation method of a kind of molecular sieve as claimed in claim 1 is characterized in that the per-cent that the middle EUO type directed agents of described step (3) accounts for the reactant cumulative volume is 10-40%.
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|---|---|---|---|
| CN 201110066897 CN102225773A (en) | 2011-03-18 | 2011-03-18 | Preparation method of molecular sieve |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183354A (en) * | 2011-12-31 | 2013-07-03 | 上海欣年石化助剂有限公司 | Method for preparing EUO structural zeolite |
| CN104229817A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of small grain molecular sieve with EUO structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796278A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Method for preparing silicon-aluminum molecular sieve in EUO structure |
| CN101054183A (en) * | 2007-04-26 | 2007-10-17 | 太原理工大学 | Method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder |
-
2011
- 2011-03-18 CN CN 201110066897 patent/CN102225773A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796278A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Method for preparing silicon-aluminum molecular sieve in EUO structure |
| CN101054183A (en) * | 2007-04-26 | 2007-10-17 | 太原理工大学 | Method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder |
Non-Patent Citations (1)
| Title |
|---|
| 《石油学报（石油加工）》 20081031 周朋燕 等 导向剂法合成EU-1分子筛 第226-229页 1-11 , * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183354A (en) * | 2011-12-31 | 2013-07-03 | 上海欣年石化助剂有限公司 | Method for preparing EUO structural zeolite |
| CN103183354B (en) * | 2011-12-31 | 2015-01-21 | 上海欣年石化助剂有限公司 | Method for preparing EUO structural zeolite |
| CN104229817A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of small grain molecular sieve with EUO structure |
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Application publication date: 20111026 |