CN103466652B - IM-5 molecular sieve and preparation method for catalyst thereof - Google Patents
IM-5 molecular sieve and preparation method for catalyst thereof Download PDFInfo
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Abstract
The invention relates to the technical field of molecular sieves and catalysts, and particularly relates to a preparation method of an IM-5 molecular sieve and a catalyst thereof. The method comprises the following steps of: synthesizing the IM-5 molecular sieve by adopting an in-situ template method, namely, synthesizing the IM-5 molecular sieve by directly preparing raw materials used for synthesizing a template agent and other raw materials used for synthesizing a molecular sieve into synthetic liquid according to certain molar ratio without synthesizing the template agent in the synthesizing process of the molecular sieve and regulating raw material ratio and reaction conditions. According to the invention, a synthesized product has higher crystallinity; incompletely reacted template agent raw materials can be recycled in a decompressing process; the obtained IM-5 molecular sieve can carry out ion exchange to obtain a hydrogen type molecular sieve catalyst. The method disclosed by the invention has the characteristics of easiness and convenience for synthetic process, easiness for operation of the synthetic process, cost saving, environment friendliness, and the like and has the characteristics of high activity, good selectivity, and the like in methanol and methylbenzene alkylation reaction.
Description
Technical field
The present invention relates to molecular sieve and catalyzer, specifically belong to the preparation method of a kind of IM-5 molecular sieve and catalyzer thereof.
Background technology
IM-5 molecular sieve is that Compaynie Francaise des Petroles was in exploitation (WO98/17581) in 1998.2007, Baerloeher group utilizes the Charge Flipping algorithm improved, and in conjunction with the powdery diffractometry of IM-5 molecular sieve and electron microscopic data, resolve topological framework (the Christian Baerlocher et al.Science of IM-5 molecular sieve first, 2007,315,1113-1116), they find that the duct of IM-5 molecular sieve is two-dimentional ten-ring cross structure, and the effective dimensions in duct is
the unique distinction of IM-5 molecular sieve is except having respectively along except the two-dimentional staggered ten-ring duct of a axle and c-axis direction, also has one along the axial short duct of b, this duct has certain restricted, and be connected with the duct in two other direction is vertical, define the duct that a size is approximately 2.5nm, the existence in this duct makes it in catalytic reaction process, both have the diffusional limitation of two-dimensional channel to molecule, can adapt to larger transition intermediate simultaneously.In addition, the thermostability of IM-5 molecular sieve, hydrothermal stability and acid feature are all better than ZSM-5, and therefore, in a lot of reaction, IM-5 molecular sieve all shows more excellent catalytic performance.Such as, in wax cracking reaction, the distribution of the reaction product that IM-5 molecular sieve and ZSM-5 molecular sieve obtain is close, but IM-5 molecular sieve shows the catalytic activity higher than ZSM-5 molecular sieve; In naphtha cracking reaction, compared with ZSM-5, the high hydrothermal stability of IM-5 molecular sieve makes it have higher catalytic activity, and meanwhile, more strong acidic site makes the olefin/paraffin ratio in the reaction product of IM-5 molecular sieve higher.Unique catalytic performance (Corma A.et al.Journal of Catalysis, 2000,189 (2): 382-394) is shown in the reactions such as n-decane isomerization.Be used for the selective catalytic reduction reaction of NO after Cu load is obtained Cu/IM-5 material on IM-5 molecular sieve, find under all test conditions, the activity of Cu/IM-5 is all higher than Cu/ZSM-5.Therefore, no matter IM-5 molecular sieve is as catalyzer or carrier, in the Industrial Catalysis such as oil and fine chemistry industry process, have important using value.
Up to the present, the research about IM-5 Zeolite synthesis is also few, and synthetic method is mainly based on the method (WO98/17581) disclosed in the patent of Compaynie Francaise des Petroles.Detailed process for template, under higher basicity condition, adopts hydrothermal method to synthesize with the bi-quaternary ammonium salt of N-methylpyrrole (1,5-bis-(N-methylpyrrole) pentane or 1,6-bis-(N-methylpyrrole) hexane).Wang L etc. by adding PEG(polyoxyethylene glycol in system) or CTAB(cetyl trimethylammonium bromide) carry out study on the synthesis (the Wang L et al.Materials Letters of IM-5 molecular sieve, 2012,69,16-19), after adding PEG and CTAB at the same time, obtain the IM-5 molecular sieve that size is approximately about 35nm.Because template required in aforesaid method is not commercially sold, can only synthesize in laboratory during use, and need to use ether to make solvent in building-up process, use washing with acetone product, therefore aforesaid method have that template building-up process is complicated, solvent volatile explosive, to shortcomings such as contaminate environment.
Summary of the invention
The object of the present invention is to provide that a kind of operating process is easy, environmental friendliness and the preparation method of the good IM-5 molecular sieve of catalytic performance and catalyzer thereof.
The preparation method of a kind of IM-5 molecular sieve provided by the invention, comprises the steps:
1) liquid preparation is synthesized: according to Al
2o
3: SiO
2: X:Y:NaOH:NaBr:H
2o mol ratio is 0.01 ~ 0.1:1:0.05 ~ 1:0.1 ~ 1:0.2 ~ 1:0 ~ 1:30 ~ 300, in room temperature and under stirring, silicon source, aluminium source, template synthesis material, Sodium Bromide, sodium hydroxide and water is hybridly prepared into synthesis liquid; Wherein X and Y is synthesis template desired raw material, and X is pentamethylene bromide or 1,6-dibromo-hexane, and Y is N-crassitude;
2) crystallization of molecular sieve: by the synthesis liquid of step 1) crystallization 4 ~ 15 days at 160 ~ 200 DEG C; After reaction terminates, with deionized water wash to neutral;
3) drying of molecular sieve and roasting: by step 2) products therefrom dry 10 ~ 12h at 100 ~ 120 DEG C, 500 ~ 580 DEG C of roasting 6 ~ 8h, obtain IM-5 molecular sieve product.
Said silicon source is tetraethoxy, silicon sol or silica gel.
Said aluminium source is pseudo-boehmite, sodium aluminate or Tai-Ace S 150.
The mol ratio of said synthesis liquid is Al
2o
3: SiO
2: X:Y:NaOH:NaBr:H
2o=0.01 ~ 0.1:1:0.05 ~ 0.5:0.1 ~ 1.:0.2 ~ 0.8:0 ~ 0.5:30 ~ 100.
Said crystallization time is 6 ~ 12 days.
The preparation method of a kind of IM-5 molecular sieve catalyst provided by the invention, detailed process is: the exchange liquid first preparing 0.1 ~ 1mol/L, and said exchange liquid is HCl, NH
4cl or NH
4nO
3solution; Claim 1 step 3) gained molecular sieve product and exchange liquid are exchanged by solid-to-liquid ratio 1:4 ~ 6, exchange temperature is 30 ~ 80 DEG C, exchanges 2 ~ 3 times, exchanges 1 ~ 4h at every turn; Exchange terminates rear centrifuge washing to neutral, and by product dry 10 ~ 12h at 100 ~ 120 DEG C, 500 ~ 580 DEG C of roasting 6 ~ 8h, obtain H-IM-5 molecular sieve catalyst.
The preparation method of IM-5 molecular sieve provided by the invention and catalyzer, adopts original position template to synthesize.Namely do not need to synthesize template in the process of synthesis, but direct preparation by certain mol ratio by other raw material of the raw material and synthesis of molecular sieve that synthesize template synthesizes liquid, by methods such as modulation synthetic ratio, reaction conditionss, obtain the pure phase IM-5 molecular sieve (relative crystallinity is greater than 90%) of high-crystallinity.In addition, unreacted completely template synthesis material can recycle and reuse in stress-relief process.The method has the features such as building-up process is simple and easy to operate, cost-saving, environmental friendliness; This zeolite product catalysis alkylation of toluene methanol reaction result is utilized to show, this molecular sieve has higher catalytic activity and selectivity, toluene conversion is greater than 55%, and the selectivity of aromatic hydrocarbons in oil phase is greater than 69%, and the selectivity of p-Xylol in aromatic hydrocarbons is greater than 41%.
Accompanying drawing explanation
Fig. 1 is the XRD(X-ray diffraction of IM-5 molecular sieve in embodiment 1) figure.
Fig. 2 is the SEM(scanning electron microscope of IM-5 molecular sieve in embodiment 1) figure.
Embodiment
Embodiment 1: by 4.5g silica gel, 0.2g sodium aluminate, 5.8g sodium hydroxide, 0.6g Sodium Bromide, 4.0g1, pentamethylene bromide, 2.0g N-methylpyrrole and 90g deionized water at room temperature stir, and obtain synthesizing liquid.The synthesis liquid prepared is proceeded in crystallizing kettle, 165 DEG C of crystallization 10 days after sealing.After crystallization completes, take out crystallizing kettle, cool fast, washing is to neutral, and at 110 DEG C, dry 12h, 550 DEG C of roasting 6h, obtain IM-5 zeolite product.Characterize by XRD, SEM technology.XRD result shows, product is IM-5 molecular sieve (as shown in Figure 1).SEM result shows this sample topography regular (as shown in Figure 2), and nitrogen adsorption result shows that its specific surface is 395m
2/ g.
Embodiment 2: 15.6g tetraethoxy, 3.08g Tai-Ace S 150,0.58g sodium hydroxide, 5.4g1,6-dibromo-hexane, 2.0g N-methylpyrrole and 54g deionized water are at room temperature stirred, obtains synthesizing liquid.The synthesis liquid prepared is proceeded in crystallizing kettle, 165 DEG C of crystallization 8 days after sealing.Washing, to neutral, dried 10h, is obtained IM-5 zeolite product after 550 DEG C of roasting 8h at 110 DEG C.
Embodiment 3: 4.5g silica gel, 0.2g sodium aluminate, 1.5g sodium hydroxide, 0.6g Sodium Bromide, 1.8g dibromo pentane, 0.9g N-methylpyrrole and 41g deionized water are at room temperature stirred, obtains synthesizing liquid.The synthesis liquid prepared is proceeded in crystallizing kettle, 180 DEG C of crystallization 10 days after sealing.After crystallization completes, take out crystallizing kettle, cool fast, washing is to neutral, and at 110 DEG C, dry 12h, 550 DEG C of roasting 6h, obtain IM-5 zeolite product.
Embodiment 4: 11.25g silicon sol (40wt%), 0.14g pseudo-boehmite (96wt%), 1.95g sodium hydroxide, 3g Sodium Bromide, 8.7g dibromo pentane, 6.2g N-methylpyrrole and 65g deionized water are at room temperature stirred, obtains synthesizing liquid.The synthesis liquid prepared is proceeded in crystallizing kettle, 180 DEG C of crystallization 8 days after sealing.Washing, to neutral, dried 12h, is obtained IM-5 zeolite product after 550 DEG C of roasting 6h at 110 DEG C.
Embodiment 5: 4.5g silica gel, 0.6g sodium aluminate, 2.5g sodium hydroxide, 3g Sodium Bromide, 9.8g1,6-dibromo-hexane, 6.2g N-methylpyrrole and 65g deionized water are at room temperature stirred, obtains synthesizing liquid.The synthesis liquid prepared is proceeded in crystallizing kettle, 200 DEG C of crystallization 6 days after sealing.Washing is to neutral, and at 110 DEG C, dry 12h, 550 DEG C of roasting 6h, obtain IM-5 zeolite product.
Embodiment: 6: 4.5g silica gel, 0.5g sodium aluminate, 2.5g sodium hydroxide, 3g Sodium Bromide, 8.7g dibromo pentane, 6.2g N-methylpyrrole and 65g deionized water are at room temperature stirred, obtains synthesizing liquid.The synthesis liquid prepared is proceeded in crystallizing kettle, 200 DEG C of crystallization 6 days after sealing.Washing is to neutral, and at 110 DEG C, dry 12h, 550 DEG C of roasting 6h, obtain IM-5 zeolite product.
Embodiment 7: the IM-5 molecular sieve obtained by embodiment 1 is become hydrogen type catalyst, and concrete steps are as follows: the NH of preparation 1mol/L
4cl solution, by 8g molecular sieve and 32g NH
4cl solution mixes, at 80 DEG C, stir 1h, then by solid-liquid separation, after repeating said process three times, by solid at 110 DEG C of dry 12h, at 550 DEG C of roasting 6h, obtains H-IM-5 molecular catalyst.By for subsequent use for gained H-IM-5 catalyzer compressing tablet to 20 ~ 40 order.With alkylation of toluene methanol reaction for probe reaction, self-control Pulse Micro-Chromatography device investigates molecular sieve catalytic alkylation properties, n
(methyl alcohol)/ n
(toluene)=2, temperature of reaction 440 DEG C, reaction pressure is 0.5MPa, and mass space velocity is 1.2h
-1, N
2be 10 with mixing raw material mol ratio.Reaction result shows, toluene conversion is 58% under this condition, and the selectivity of aromatic hydrocarbons in oil phase is 71%, and the selectivity of p-Xylol in aromatic hydrocarbons is 41%.
Embodiment 8: the IM-5 molecular sieve obtained by embodiment 4 is become hydrogen type catalyst, and concrete steps are as follows: the NH of preparation 1mol/L
4nO
3solution, other conditions are with embodiment 7.Toluene conversion is 58% under this condition, and the selectivity of aromatic hydrocarbons in oil phase is 69%, and the selectivity of p-Xylol in aromatic hydrocarbons is 41%.
Embodiment 9: the IM-5 molecular sieve obtained by embodiment 2 is become hydrogen type catalyst, concrete steps are as follows: the HCl solution of preparation 0.2mol/L, 8g molecular sieve is mixed with the HCl solution that 40g prepares, 1h is stirred at 60 DEG C, then by solid-liquid separation, after repeating said process three times, by solid at 110 DEG C of dry 12h, at 550 DEG C of roasting 6h, obtain H-IM-5 molecular sieve catalyst.By gained H-IM-5 catalyzer compressing tablet and to be sized to 20 ~ 40 orders for subsequent use.With alkylation of toluene methanol reaction for probe reaction, self-control Pulse Micro-Chromatography device investigates molecular sieve catalytic alkylation properties, n (methyl alcohol)/n (toluene)=2, temperature of reaction 440 DEG C, reaction pressure is 0.5MPa, mass space velocity is 1.2h-1, N2 and mixing raw material mol ratio is 10.Reaction result shows, toluene conversion is 55% under this condition, and the selectivity of aromatic hydrocarbons in oil phase is 74%, and the selectivity of p-Xylol in aromatic hydrocarbons is 42%.
Claims (2)
1. the synthetic method of an IM-5 molecular sieve, it is characterized in that, 15.6g tetraethoxy, 3.08g Tai-Ace S 150,0.58g sodium hydroxide, 5.4g 1,6-dibromo-hexane, 2.0g N-methylpyrrole and 54g deionized water are at room temperature stirred, obtains synthesizing liquid; Synthesis liquid is proceeded in crystallizing kettle, 165 DEG C of crystallization 8 days after sealing; Washing, to neutral, dried 10h, is obtained IM-5 zeolite product after 550 DEG C of roasting 8h at 110 DEG C.
2. the synthetic method of an IM-5 molecular sieve, it is characterized in that, 4.5g silica gel, 0.6g sodium aluminate, 2.5g sodium hydroxide, 3g Sodium Bromide, 9.8g 1,6-dibromo-hexane, 6.2g N-methylpyrrole and 65g deionized water are at room temperature stirred, obtains synthesizing liquid; Synthesis liquid is proceeded in crystallizing kettle, 200 DEG C of crystallization 6 days after sealing; Washing is to neutral, and at 110 DEG C, dry 12h, 550 DEG C of roasting 6h, obtain IM-5 zeolite product.
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| CN105272797B (en) * | 2014-06-03 | 2017-05-24 | 中国石油化工股份有限公司 | Benzene and methanol alkylation reaction method |
| CN105315120B (en) * | 2014-06-03 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method that benzene reacts with methanol alkylation |
| CN109593020B (en) * | 2017-09-30 | 2022-04-08 | 中国石油化工股份有限公司 | Alkylation reaction method |
| CN110407228B (en) * | 2018-04-26 | 2021-04-06 | 中国石油化工股份有限公司 | Method for synthesizing IM-5 molecular sieve |
| CN111977668B (en) * | 2019-05-22 | 2022-08-30 | 中国石油天然气股份有限公司 | IM-5 molecular sieve and preparation method thereof |
| CN117800357A (en) * | 2024-01-05 | 2024-04-02 | 陕西探微日新化工有限公司 | IM-5 molecular sieve synthesis method and modification method |
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| CN102205251A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Molecular sieve P-IM-5 and its application in toluene alkylation reaction |
| CN102452666A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for synthesizing IM-5 molecular sieve |
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| CN102205251A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Molecular sieve P-IM-5 and its application in toluene alkylation reaction |
| CN102452666A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for synthesizing IM-5 molecular sieve |
Non-Patent Citations (1)
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