CN104724722A - Method for treatment of molecular sieve by fluorine-containing alkaline medium - Google Patents

Method for treatment of molecular sieve by fluorine-containing alkaline medium Download PDF

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CN104724722A
CN104724722A CN201310704413.3A CN201310704413A CN104724722A CN 104724722 A CN104724722 A CN 104724722A CN 201310704413 A CN201310704413 A CN 201310704413A CN 104724722 A CN104724722 A CN 104724722A
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molecular sieve
fluorine
alkaline medium
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medium process
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CN104724722B (en
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黄声骏
徐龙伢
于丽丽
陈福存
刘珍妮
谢素娟
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Dalian Institute of Chemical Physics of CAS
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Abstract

Belonging to the field of molecular sieve modification, adsorption material preparation and catalyst preparation, the invention relates to a method for treatment of a molecular sieve by a fluorine-containing alkaline medium. The method includes: introducing fluorine element into a molecular sieve alkaline treatment medium in a certain way, then conducting heating treatment, performing filtering and washing to neutral, conducting drying, and then carrying out ion exchange and roasting process to exchange into a hydrogen type molecular sieve. The method is easy to operate and is low in cost. The obtained modified molecular sieve material has well maintained micropores, generates rich secondary pore structure, and at the same time maintains good acidity.

Description

A kind of method of fluorine-containing alkaline medium process molecular sieve
Technical field
The invention belongs to the preparation of molecular sieve modified, sorbing material and field of catalyst preparation, be specifically related to a kind of method of fluorine-containing alkaline medium process molecular sieve
Background technology
Since molecular sieve comes out, because it has abundant microvoid structure, the features such as good hydrothermal stability and strongly-acid, have been widely used in the catalytic fields such as refining of petroleum, Coal Chemical Industry, environment protection and fine chemistry industry as catalysis, adsorption and separation material.Especially ZSM-5, mordenite equimolecular sieve are widely used in cracking, isomery, alkylation, in the reaction such as aromizing.Because microporous molecular mesh size is less, there is the problem such as absorption, diffusional limitation, easily carbon distribution in the reaction, improve its pore structure and Acidity distribution becomes the effective ways solving these difficult problems.
At present, the industrial method improved Molecular Sieve Pore and Acidity is mainly chemical after-treatment logos.US5118482 discloses one and utilizes basic solution (NaOH, KOH or ammonia soln) to carry out immersion treatment, to improve the method for Al content in molecular sieve to L, FER, mordenite equimolecular sieve.US5118482 discloses US6184167 and discloses a kind of use NaOH or sodium carbonate (Na 2cO 3) method to ZSM-5 process.US5952259 discloses a kind of method utilizing basic solution process-acidic solution reprocessing molecular sieve to be carried out to modification.People's detailed examination such as JavierP é rez-Ram í rez utilize sodium hydroxide (NaOH) solution to carry out immersion treatment to the micro porous molecular sieve of Si/Al ratio within the scope of 25-50 at a certain temperature, form secondary pore structure (Chem.Eur.J.2005,11,4983-4994).But the characteristic of alkali treatment method is in above-mentioned molecular sieve post-treating method: use alkaline purification medium to be simple basic solution, the adjustment of the secondary pore structure of molecular sieve is placed one's entire reliance upon the temperature (60-90 DEG C) of alkaline purification process and concentration (0.2-5.0 mol/L).But the concentration of the simple treatment temp and process alkali lye that raise soda ash liquid causes secondary pore aperture to become large, high concentration basic solution very easily causes a large amount of dissolving of molecular sieve and microvoid structure to destroy simultaneously, this makes the adjustability of basic treatment method limited, and application is restricted.
The present invention by introducing fluorine-containing material in alkaline medium, change alkaline medium to the dissolving power of Si-Al molecular sieve, realize forming to the secondary pore structure of molecular sieve the object regulated, the molecular screen material obtained produces secondary pore distribution between 2nm-20nm.The molecular sieve being applicable to fluorine-containing alkaline medium comprises: for topological framework be MFI, Si/Al atomic ratio between 10-100, Na 2the ZSM-5 molecular sieve of O content 0-3.0wt%; Topological framework be MEL, Si/Al atomic ratio between 10-100, Na 2the ZSM-5 molecular sieve of O content 0-2.8wt%; Topological framework be MOR, Si/Al atomic ratio between 15-50, Na 2the mordenite of O content 0-4wt%.
Summary of the invention
The object of the present invention is to provide a kind of method of fluorine-containing alkaline medium process molecular sieve, the dissolving power of alkaline medium to Si-Al molecular sieve is regulated and controled by using the basic treatment medium of fluorine-containing material, secondary pore structure through process institute acquisition molecular sieve is adjustable, and is obviously different from the pore structure of floride-free alkali lye media processes gained molecular sieve.Step of the present invention is simple, has good industrial applications prospect.
The invention provides a kind of method of fluorine-containing alkaline medium process molecular sieve, the method step is: dropped into by molecular sieve in fluorine-containing alkaline medium solution by a certain percentage, the suspension of molecular sieve and fluorine-containing alkaline medium is stirred, and being warming up to 50-90 DEG C, the duration of heat is between 5 minutes-180 minutes; By the sample filtering washing after above-mentioned process to neutral, dry, then at 350-600 DEG C of roasting 3-6h, carry out ammonium exchange, roasting more afterwards, finally change hydrogen type molecular sieve into;
Wherein, the ratio (liquid volume/solid masses) (normally used is exactly solid-to-liquid ratio, is exactly the solution of corresponding how many milliliters of 1g solid) of fluorine-containing alkaline medium and molecular sieve is between 5-120.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, described fluorine-containing alkaline medium is the mixing solutions of alkaline matter and fluorochemicals;
Wherein, the amount of substance ratio of alkaline matter and fluorochemicals is between 2-30.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, with negatively charged ion (OH-, CO 3 2-) concentration calculating, the concentration of described alkaline matter is between 0.02-1.0mol/L.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, calculate with F ion concentration, the concentration of described fluorochemicals is between 0.005-0.2mol/L.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, alkaline matter is NaOH, KOH, Na 2cO 3, K 2cO 3in one or more.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, described fluorochemicals is NH 4f, NaF, KF, (NH 4) 2siF 6in one or more.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, described molecular sieve is MFI(ZSM-5), MEL(ZSM-11), MOR(mordenite) in one or more.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, the silica alumina ratio Si/Al scope of described ZSM-5 molecular sieve between 10-100, sodium oxide (Na 2o) massfraction (wt%) is 0-3.0wt%.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, the silica alumina ratio Si/Al scope of described ZSM-11 molecular sieve between 10-100, sodium oxide (Na 2o) content is 0-2.8wt%.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, the Si/Al scope of described mordenite molecular sieve between 15-50, sodium oxide (Na 2o) content is 0-4wt%.
The method of fluorine-containing alkaline medium process molecular sieve provided by the invention, the state that molecular sieve comprises fluorine material in advance can be dry mixed by dipping or machinery, then obtains in the method for 250-600 DEG C of roasting.
Accompanying drawing explanation
Fig. 1 is the secondary pore distribution curve of fluorine-containing alkaline medium process ZSM-5 molecular sieve sample in the embodiment of the present invention 1;
Fig. 2 is the secondary pore distribution curve of sample after the embodiment of the present invention 5 fluorine-containing alkaline medium process ZSM-5 molecular sieve;
Fig. 3 is the secondary pore distribution curve of sample after fluorine-containing alkaline medium process ZSM-5 molecular sieve in the embodiment of the present invention 6;
Fig. 4 is the secondary pore distribution curve of floride-free alkaline medium process ZSM-5 molecular sieve in comparative example 1 of the present invention.
Embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
Get 10g ZSM-5 molecular sieve (Si/Al=40, Na 2o content <0.02wt%) join 100ml and contain 0.25mol/L NaOH-0.03mol/L NH 4in F solution, 60 DEG C of lower magnetic forces stir 35 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 550 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.8mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:20, and 85 DEG C of lower magnetic forces stir 2 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 550 DEG C in retort furnace afterwards, is designated as sample A.
Embodiment 2
Get 15g ZSM-5 molecular sieve (Si/Al=37, Na 2o content 0.25wt%) join 200ml and contain 0.25mol/L KOH-0.05mol/L NH 4in the mixing solutions of F, 80 DEG C of lower magnetic forces stir 60 minutes, and then filtration washing is to neutral, and 110 DEG C of dryings are roasting 3 hours at 540 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.8mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:20, and 85 DEG C of lower magnetic forces stir 2 hours, then filtration washing, dry 12h at 120 DEG C, and roasting 6 hours at 550 DEG C in retort furnace afterwards, is designated as sample B.
Embodiment 3
Get 150g ZSM-5 molecular sieve (Si/Al=60, Na 2o content 0.09wt%) join 1800ml and contain in the mixing solutions of 0.15mol/L NaOH-0.02mol/L KF, 55 DEG C of lower magnetic forces stir 60 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 530 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.8mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:10, and 80 DEG C of lower magnetic forces stir 2 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 530 DEG C in retort furnace afterwards, is designated as sample C.
Embodiment 4
Get 150g ZSM-5 molecular sieve (Si/Al=90, Na 2o content <0.02wt%) join 2000ml and contain 0.12mol/L NaOH-0.01mol/L NH 4in the mixing solutions of F, 65 DEG C of lower magnetic forces stir 40 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 510 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.8mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:20, and 90 DEG C of lower magnetic forces stir 2 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 530 DEG C in retort furnace afterwards, is designated as sample D.
Embodiment 5
Get 40g ZSM-5 molecular sieve (Si/Al=16, Na 2o content <0.02wt%), after adding 1.0g Neutral ammonium fluoride, add 200ml deionized water dissolving, then room temperature magnetic agitation 8 hours, 120 DEG C of dryings are roasting 3 hours at 500 DEG C in retort furnace after 12 hours.Molecular sieve after roasting is joined 3000ml and contains 0.4mol/L Na 2cO 3in the mixing solutions of-0.03mol/L NaF, 85 DEG C of lower magnetic forces stir 30 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 550 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.90mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:30, and 90 DEG C of lower magnetic forces stir 2 hours, then filtration washing, dry dry 12 hours at 120 DEG C, and roasting 6 hours at 510 DEG C in retort furnace afterwards, is designated as sample E.
Embodiment 6
Get 40g ZSM-5 molecular sieve (Si/Al=17, Na 2o content 0.6wt%), after adding 0.8gNaF, mechanically mixing evenly after roasting 3 hours at 500 DEG C in retort furnace.Molecular sieve after roasting is joined 4000ml and contains 0.30mol/L K 2cO 3in the mixing solutions of-0.03mol/L NaF, 85 DEG C of lower magnetic forces stir 30 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 550 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.90mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:30, and 90 DEG C of lower magnetic forces stir 2 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 510 DEG C in retort furnace afterwards, is designated as sample F.
Embodiment 7
Get 30g ZSM-11 molecular sieve (Si/Al=50, Na 2o content <0.02wt%) join 600ml and contain 0.25mol/L NaOH-0.02mol/L NH 4in F solution, 70 DEG C of lower magnetic forces stir 35 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 550 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.6mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:20, and 90 DEG C of lower magnetic forces stir 2 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 550 DEG C in retort furnace afterwards, is designated as sample G.
Embodiment 8
Get 40g ZSM-11 molecular sieve (Si/Al=23, Na 2o content 1.5wt%) join 500ml and contain 0.15mol/L NaOH-0.04mol/L NH 4in F solution, 80 DEG C of lower magnetic forces stir 120 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 550 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.9mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:20, and 85 DEG C of lower magnetic forces stir 2 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 530 DEG C in retort furnace afterwards, is designated as sample H.
Embodiment 9
Get 80g mordenite (Si/Al=3,0Na 2o content 1.3wt%), add 8.9g (NH 4) 2siF 6and add 100ml deionized water dissolving, then in 50 DEG C of magnetic agitation 3 hours, filter, 110 DEG C of dryings 12 hours, 560 DEG C of roastings 3 hours.Obtained molecular sieve is joined 2800ml and contain 0.45mol/L NaOH-0.03mol/L NH 4in F solution, 85 DEG C of lower magnetic forces stir 120 minutes, and then centrifuge washing is to neutral, and 120 DEG C of dryings are roasting 3 hours at 550 DEG C in retort furnace after 12 hours.Join in the ammonium nitrate solution of 0.9mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:30, and 85 DEG C of lower magnetic forces stir 1.5 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 530 DEG C in retort furnace afterwards, is designated as sample I.
Embodiment 10
Get 30g mordenite (Si/Al=17, Na 2o content 3.3wt%), add 2.2g (NH 4) 2siF 6and add 100ml deionized water dissolving, then in 50 DEG C of magnetic agitation 3 hours, filter, 110 DEG C of dryings 12 hours, 360 DEG C of roastings 3 hours.Obtained molecular sieve is joined 1800ml and contain 0.25mol/L NaOH-0.04mol/L NH 4in F solution, 80 DEG C of lower magnetic forces stir 150 minutes, and then centrifuge washing is to neutral, roasting 3 hours at 550 DEG C in retort furnace after 120 DEG C of dry 12h.Join in the ammonium nitrate solution of 0.9mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:30, and 85 DEG C of lower magnetic forces stir 1.5 hours, then filtration washing, at 120 DEG C dry 12 hours, and roasting 6 hours at 530 DEG C in retort furnace afterwards, is designated as J.
Comparative example 1(comparative example is the secondary pore structure of floride-free alkaline medium process molecular sieve, can produce obviously contrast with fluoro-containing medium)
Get 10g ZSM-5 molecular sieve (Si/Al=35, Na 2o content <0.02wt%) join 300ml and contain in 0.2mol/L NaOH solution, 65 DEG C of lower magnetic forces stir 30 minutes, and then filtration washing is to neutral, and 120 DEG C of dryings are after 12 hours, roasting 3 hours at 550 DEG C in retort furnace.Join in the ammonium nitrate solution of 0.8mol/L by obtained molecular sieve, solid-to-liquid ratio is 1:10, and 85 DEG C of lower magnetic forces stir 2 hours, then filtration washing, at 120 DEG C dry 12 hours, roasting 6 hours at 550 DEG C in retort furnace afterwards.
After fluorine-containing alkaline medium process, specific surface area and total pore volume of molecular sieve all increase significantly; Fluorine-containing alkaline medium produces concentrated secondary pore (embodiment 1,5,6) within the scope of 2-10nm, and floride-free medium only can at 10nm and the moderate secondary pore (comparative example 1) of above generation thereof
Table 1 fluorine-containing alkaline medium process molecular sieve structure data
Continuous upper table:
Continuous upper table:

Claims (11)

1. a method for fluorine-containing alkaline medium process molecular sieve, is characterized in that: the method step is:
Dropped into by molecular sieve in fluorine-containing alkaline medium solution by a certain percentage, stirred by the suspension of molecular sieve and fluorine-containing alkaline medium, and be warming up to 50-90 DEG C, the duration of heat is between 5 minutes-180 minutes; By the sample filtering washing after above-mentioned process to neutral, dry, then at 350-600 DEG C of roasting 3-6h, carry out ammonium exchange, roasting more afterwards, finally change hydrogen type molecular sieve into;
Wherein, the ratio of fluorine-containing alkaline medium and molecular sieve is between 5-120.
2., according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 1, it is characterized in that: described fluorine-containing alkaline medium is the mixing solutions of alkaline matter and fluorochemicals;
Wherein, the amount of substance ratio of alkaline matter and fluorochemicals is between 2-30.
3. according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 1, it is characterized in that: calculate with anion concentration, the concentration of described alkaline matter is between 0.02-1.0mol/L.
4. according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 1, it is characterized in that: calculate with F ion concentration, the concentration of described fluorochemicals is between 0.005-0.2mol/L.
5., according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 2, it is characterized in that: described alkaline matter is NaOH, KOH, Na 2cO 3, K 2cO 3in one or more.
6., according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 2, it is characterized in that: described fluorochemicals is NH 4f, NaF, KF, (NH 4) 2siF 6in one or more.
7., according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 1, it is characterized in that: described molecular sieve is the one in ZSM-5, ZSM-11, mordenite.
8. according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 7, it is characterized in that: the silica alumina ratio Si/Al scope of described ZSM-5 molecular sieve is between 10-100, and sodium oxide mass percentage is 0-3.0wt%.
9. according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 7, it is characterized in that: the silica alumina ratio Si/Al scope of described ZSM-11 molecular sieve is between 10-100, and sodium oxide mass percentage is 0-2.8wt%.
10. according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 7, it is characterized in that: the Si/Al scope of described mordenite molecular sieve is between 15-50, and sodium oxide mass percentage is 0-4wt%.
11., according to the method for alkaline medium process molecular sieve fluorine-containing described in claim 1, is characterized in that: can with by dipping in molecular sieve, and mechanical mix techniques is introducing portion fluorine cpd in advance, then carry out roasting the temperature of 250-600 DEG C.
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CN107790174A (en) * 2017-10-12 2018-03-13 河南师范大学 Modified molecular sieve catalysts of H ZSM 11 and its preparation method and application
CN109835914A (en) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 A method of it is combined by heat partition and alkali process and prepares multistage porous molecular sieve
CN111250153A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation
CN114073976A (en) * 2020-08-10 2022-02-22 中国科学院大连化学物理研究所 Modified ZSM-5 molecular sieve and preparation method and application thereof

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CN1240656C (en) * 2003-12-12 2006-02-08 宁夏大学 Method for gas catalytic synthesis of para-methyl methyl phenate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107790174A (en) * 2017-10-12 2018-03-13 河南师范大学 Modified molecular sieve catalysts of H ZSM 11 and its preparation method and application
CN109835914A (en) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 A method of it is combined by heat partition and alkali process and prepares multistage porous molecular sieve
CN109835914B (en) * 2017-11-28 2022-02-11 中国科学院大连化学物理研究所 Method for preparing hierarchical pore molecular sieve by combining thermal dispersion and alkali treatment
CN111250153A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation
CN111250153B (en) * 2018-11-30 2021-08-10 中国科学院大连化学物理研究所 Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation
CN114073976A (en) * 2020-08-10 2022-02-22 中国科学院大连化学物理研究所 Modified ZSM-5 molecular sieve and preparation method and application thereof

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