CN102464336A - Modification method of ZSM-5 zeolite - Google Patents
Modification method of ZSM-5 zeolite Download PDFInfo
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- CN102464336A CN102464336A CN2010105390551A CN201010539055A CN102464336A CN 102464336 A CN102464336 A CN 102464336A CN 2010105390551 A CN2010105390551 A CN 2010105390551A CN 201010539055 A CN201010539055 A CN 201010539055A CN 102464336 A CN102464336 A CN 102464336A
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Abstract
The invention discloses a modification method of a ZSM-5 zeolite. The method comprises: in a closed system containing a low molecular weight organic solvent, first treating a ZSM-5 zeolite with an alkali solution; then treating a ZSM-5 zeolite with an acid solution, and finally conducting separation, washing and drying so as to obtain a modified ZSM-5 zeolite. In the zeolite modification method provided in the invention, the organic solvent added during alkali treatment can promote the generation of a mesoporous structure so as to make a micropore structure convert to a meso-pore efficiently, and can stablize and protect the micropore structure. The subsequent acid treatment can elute amorphous aluminum in a zeolite crystal so as to reach the purposes of dredging pore channels and increasing the total specific surface area. Therefore, the method of the invention can reserve more complete micropores in the ZSM-5 zeolite and provide more mesopores, and simultaneously can increase the total BET (Brunauer-Emmett-Teller) specific surface area.
Description
Technical field
The present invention relates to a kind of Zeolite modifying method, belong to molecular sieve synthesis modification field, a kind of specifically aftertreatment method of modifying of ZSM-5 zeolite.
Background technology
The ZSM-5 zeolite is because of its regular microvoid structure, proper acidic, and good thermostability and hydrothermal stability are able to be widely used in petroleum industry.The ZSM-5 zeolite has two kinds of pore canal system that cross one another, and the aperture is respectively 5.1 * 5.5nm and 5.3 * 5.6nm, is typical microvoid structure.Micropore ZSM-5 zeolite is in relating to macromolecular reaction; Very easily the induce reaction mass transfer diffusional resistance of material of its narrow duct (less than 2nm) is excessive; React inside, macromolecular reaction thing crystal extremely difficult to get access duct, so just can not give full play to the catalysis efficiency of zeolite; And the macromole product is the internal divergence comparatively difficulty of coming out also from the duct, and very easily coking causes catalyst deactivation.In order to solve the diffusion problem of macromolecular substance in the narrow duct of micropore ZSM-5 zeolite crystal, generally take two kinds of approach: the one, the aftertreatment modification enlarges the bore dia of molecular sieve; The 2nd, synthesizing small-grain molecular sieve, the diffusion path of shortening reactant.But the separation of small-grain ZSM-5 zeolite at present is also very difficult, and very easily sintering gathering again in the high-temperature catalytic process, thereby has limited it in Industrial Application.Aftertreatment modification to the ZSM-5 zeolite is an extremely successful effective means in the industrial application.In numerous aftertreatment method of modifying, it is a relatively more novel zeolite aftertreatment method of modifying that zeolite is carried out alkaline purification, and its treatment effect is very outstanding, and is easy and simple to handle, do not need specific installation, and with low cost, prospects for commercial application is boundless.
" Appl Catal " (2001; 219:33-43) the NaOH solution-treated ZSM-5 zeolite 300min of employing 0.2mol/L; In zeolite crystal, formed more regular meso-hole structure through the element silicon in the alkali selectively removing zeolite framework, mesoporous specific surface area is from 6.6m after the modification
2/ g is increased to 115.4m
2/ g, micropore specific area are then from 296.4m
2/ g is reduced to 205m
2/ g.Though it is more that micropore specific area keeps, mesoporous content is also lower.
Patent CN101428817A handles the ZSM-5 zeolite 10～48 hours in 20～90 ℃ with the alkaline solution of 0.1～5mol/L, and obtaining a kind of diameter is the ZSM-5 zeolite of the big cavity structure of 160～190nm, and mesoporous specific surface area is the highest can reach 217m for it
2About/g, but its micropore specific area is seriously damaged, and 141.3m is only arranged
2/ g can reduce the reactive behavior of zeolite so greatly.
Patent CN1530322A handles the ZSM-5 zeolite 1～7 hour in 50～100 ℃ with the alkaline solution of 0.1～0.5mol/L, the highlyest can obtain 250m
2The mesoporous specific surface area of/g is at present the highest, but its microvoid structure also is to destroy seriously.
At present; Document and the patent reported about the alkaline purification of ZSM-5 zeolite; Main purpose is to make mesoporous with the part microvoid structure of alkali destruction ZSM-5 zeolite; Improve mesoporous specific surface area, the internal diffusion of material in zeolite crystal improved in the aperture that enlarges the ZSM-5 zeolite, thereby reaches the purpose that improves catalytic performance.Yet prior art also has two significant disadvantages: the one, and mesoporous specific surface area is also lower, and that the highest is CN1530322A, near 250m
2/ g; The 2nd, higher mesoporous the time when obtaining, the microporous crystal structure deteriorate of ZSM-5 zeolite is more serious, and micropore surface amassed low, and this can the serious catalytic activity that reduces zeolite.So higher mesoporous specific surface area is provided, the ZSM-5 zeolitic material of the microvoid structure that is kept perfectly awaits to develop.
Summary of the invention
The present invention is directed to the weak point of prior art, invented one and aimed to provide higher mesoporous specific surface area, and the method for modifying of the ZSM-5 zeolite of the microvoid structure that is kept perfectly.
The method of modifying of ZSM-5 zeolite provided by the invention mainly comprises alkaline purification and s.t..The alkaline purification process mainly act on be alkali in the closed environment that contains the lower molecular weight organic solvent, the element silicon in the selectively removing zeolite framework and in zeolite crystal, formed mesopore orbit, and keep the microporous crystal structure of original ZSM-5 zeolite; The s.t. process then is the amorphous aluminium in the wash-out zeolite crystal, thereby reaches the purpose in mediation duct.
The method of modifying of ZSM-5 zeolite of the present invention may further comprise the steps:
(1) get the ZSM-5 zeolite, the liquid-solid ratio adding alkaline solution according to 8～100mL/g stirs 0～60min under room temperature;
(2) mixture that step (1) is obtained places encloses container, according to the liquid-solid ratio adding lower molecular weight organic solvent of 0.5～10mL/g, handles 0.5～7h in 30～180 ℃;
(3) step (2) gained mixture is separated and wash;
(4) the ZSM-5 zeolite after the resulting alkaline purification of step (3) is mixed according to certain proportioning with acid solution, under room temperature, stir 5～60min, then at 40～150 ℃ of following stir process 0.5～7h;
(5) products therefrom that obtains of step (4) is through separating, wash, be drying to obtain the ZSM-5 zeolite after the modification processing.
According to the method for modifying of ZSM-5 zeolite of the present invention, wherein the alkaline solution described in the step (1) can be a kind of or several kinds the mixing solutions in NaOH, KOH, the LiOH aqueous solution.The concentration of alkaline solution is 0.1～7mol/L, preferred 0.2～2mol/L; The liquid-solid ratio that adds alkaline solution and ZSM-5 is 8～100mL/g, preferred 10～80mL/g.Preferably after adding alkaline solution, stir for some time, churning time is generally 10～60min, preferably stirs 20～40min.
Alkaline purification process in the step (2) is carried out in encloses container.Said its alkali purification temp is 30～180 ℃, preferred 40～120 ℃; Treatment time is generally 0.5～7h, preferred 2～4h.
The liquid-solid ratio that adds lower molecular weight organic solvent and ZSM-5 zeolite described in the step (2) is 0.5～10mL/g, preferred 1～5mL/g.Said organic solvent is meant that generally carbonatoms is 1～4 pure and mild ketone, is selected from methyl alcohol, ethanol, propyl alcohol, Virahol and the acetone one or more usually.
Separation described in the step (3) and washing are routine operation well known to those skilled in the art.Can take filtering method as separating, washing generally is meant uses deionized water wash.Step generally includes separating for several times and washing operation in (3), is generally 1～6 time.
Acid solution described in the step (4) can be a kind of or several kinds the mixing solutions in sulfuric acid, hydrochloric acid and the salpeter solution.The concentration of acid solution is generally 0.1～3mol/L, preferred 0.2～2mol/L.The liquid-solid ratio of said acid solution and ZSM-5 zeolite is 20～100mL/g, is preferably 30～80mL/g.
Churning time is 5～60min described in the step (4), preferred 20～40min.Said acid-treated temperature is 40～150 ℃, preferred 50～120 ℃; Treatment time is 0.5～7h, preferred 2～5h.
The ZSM-5 zeolite that carries out after modification is handled according to method of the present invention has following characteristic: this material has the XRD characteristic spectrogram of ZSM-5 zeolite; At N
2The measured aperture of adsorption-desorption exists mesoporous aperture to concentrate, and the most probable aperture is 3.5nm, and mesoporous specific surface area is 200～300m
2/ g, micropore specific area are 220～270m
2/ g.
Compared with prior art, ZSM-5 Zeolite modifying method of the present invention has following characteristics:
ZSM-5 Zeolite modifying method provided by the invention can form meso-hole structure in ZSM-5 micro-pore zeolite crystal, mesoporous specific surface area is the highest can to reach 300m
2/ g exceeds 50m than the peak of prior art
2/ g improves about 25%; Method of modifying of the present invention, the microvoid structure that can when obtaining higher mesoporous specific surface area, can also be kept perfectly, its micropore specific area can keep 220m at least
2/ g is much higher than prior art; And after handling through modification, the BET surface-area of ZSM-5 zeolite also has significantly lifting.
In the prior art, to the alkaline purification of ZSM-5 zeolite, mainly be to rely on the microvoid structure of alkaline solution destruction zeolite and produce a large amount of losses that mesoporous, such consequence must be brought micropore, reduce the chain carrier of zeolite.And alkali modification treatment process provided by the invention is airtight, exists to carry out in the environment of lower molecular weight organic solvent.In the alkaline purification process of zeolite, the lower molecular weight organic solvent of adding can promote the generation of meso-hole structure, and it is mesoporous to make that microvoid structure changes into more efficiently, also microvoid structure is played stable provide protection simultaneously.Alkaline solution optionally removes the part element silicon in the ZSM-5 zeolite crystal, makes part microvoid structure recurring structure reset and form mesoporous; S.t. process after the alkaline purification, the amorphous aluminium in can the wash-out zeolite crystal, thus reach mediation duct and the purpose that increases total specific surface area.Therefore ZSM-5 Zeolite modifying method of the present invention can keep more complete micropore, provides more how mesoporous, but also can increase total BET specific surface area.
Description of drawings
The XRD spectra of the ZSM-5 modified zeolite that Fig. 1 obtains for embodiment 1.
The graph of pore diameter distribution of the ZSM-5 modified zeolite that Fig. 2 obtains for embodiment 1.
Embodiment
In the inventive method, the D/max-2500 type that the crystalline structure of modified ZSM-5 zeolite sample adopts Japanese Co., Ltd. of science to produce automatically rotates the target x-ray diffractometer and characterizes.Experiment condition: the Cu target, K α source of radiation, graphite monochromator, WV 40kV, tube current 80mA, sweep limit is 5～40 °, and sweep velocity is 8 °/min, and step-length is 0.1 °.
The porous of sample is carried out on the ASAP2420 physical adsorption appearance that U.S. Mai Ke company produces.Experiment condition is: sample is at 300 ℃, and the degassing is 4 hours under the 0.1MPa condition, treats to take off sample after sample bottle charges into the nitrogen of 101.325kPa, accurately analyzes after the weighing.Total specific surface area gets according to BET thermo-isopleth Equation for Calculating, and micro pore volume and outer surface area are tried to achieve according to the t-Plot graphing method, and pore size distribution adopts the BJH method to calculate.
Through specific embodiment ZSM-5 Zeolite modifying method of the present invention is given detailed description below, but be not limited to embodiment.
The raw material ZSM-5 zeolite that uses in the embodiment of the invention is available from Fushun No.3 Petroleum Factory, and its silica alumina ratio is 18.7, and the BET specific surface area is 364m
2/ g, micropore specific area are 298m
2/ g, mesoporous specific surface area is 66m
2/ g.Employed acid, alkali and solvent are the analytical pure chemical reagent.
Embodiment 1
The NaOH solution 2400mL that gets 30g ZSM-5 zeolite, 0.30mol/L places beaker, stirs 30min down in room temperature condition, changes in the closed reactor, adds the methyl alcohol of 75mL again, handles 4h, filtration, washing in 60 ℃.ZSM-5 zeolite after the washing is placed beaker, and adding 0.2mol/L hydrochloric acid soln 1500mL stirs 20min down in room temperature condition, changes 70 ℃ of processing 3h in the water-bath over to, filters, washs, and places 110 ℃ of dry 12h of baking oven again, and the gained sample number into spectrum is CL1.
Can find out that by Fig. 1 the CL1 sample has the XRD characteristic spectrogram of ZSM-5 zeolite, still keeps good ZSM-5 zeolite structured.Can find out that by Fig. 2 after handling through modification, in the ZSM-5 zeolite, exist significantly mesoporous aperture to concentrate, the most probable aperture is 3.5nm.
Embodiment 2
The KOH solution 40mL that gets 1g ZSM-5 zeolite, 0.60mol/L places beaker, stirs 30min down in room temperature condition, changes in the closed reactor, adds the ethanol of 3mL again, handles 3h, filtration, washing in 80 ℃.ZSM-5 zeolite after the washing is placed beaker, and adding 0.2mol/L salpeter solution 30mL stirs 20min down in room temperature condition, changes 90 ℃ of processing 2h in the water-bath over to, filters, washs, and places 110 ℃ of dry 12h of baking oven again, and the gained sample number into spectrum is CL2.
Embodiment 3
The NaOH solution 70mL that gets 1g ZSM-5 zeolite, 0.50mol/L places beaker, stirs 30min down in room temperature condition; Change over to then in the closed reactor, add the propyl alcohol of 5mL again, handle 4h in 100 ℃; Filter, wash; ZSM-5 zeolite after the washing is placed beaker, and the sulphuric acid soln 50mL of adding 0.8mol/L stirs 30min down in room temperature condition, changes 90 ℃ of processing 3h in the water-bath over to, filters, washs, and places 110 ℃ of dry 12h of baking oven again, and the gained sample number into spectrum is CL3.
Embodiment 4
The LiOH solution 80mL that gets 1g ZSM-5 zeolite, 0.20mol/L places beaker, stirs 40min down in room temperature condition, changes in the closed reactor, adds the propyl alcohol of 2mL again, handles 2h, filtration, washing in 120 ℃.ZSM-5 zeolite after the washing is placed beaker, and adding 0.5mol/L sulphuric acid soln 30mL stirs 20min down in room temperature condition, changes 100 ℃ of processing 3h in the water-bath over to, filters, washs, and places 110 ℃ of dry 12h of baking oven again, and the gained sample number into spectrum is CL4.
Embodiment 5
The NaOH solution 70mL that gets 1g ZSM-5 zeolite, 0.35mol/L places beaker, stirs 30min down in room temperature condition, changes in the closed reactor, adds the propyl alcohol of 2mL again, handles 3.5h, filtration, washing in 50 ℃.ZSM-5 zeolite after the washing is placed beaker, and adding 0.5mol/L sulphuric acid soln 40mL stirs 40min down in room temperature condition, changes 80 ℃ of processing 3h in the water-bath over to, filters, washs, and places 110 ℃ of dry 12h of baking oven again, and the gained sample number into spectrum is CL5.
Comparative example 1
According to method described in the CN101428817A ZSM-5 zeolite being carried out modification handles.The NaOH solution 3000mL that gets 30gZSM-5 zeolite, 0.10mol/L places beaker, stirs 30min down in room temperature condition.Change in the flask again, under refluxing, in 60 ℃ of stirrings 12 hours, filter, wash, place 110 ℃ of dry 12h again, the gained sample number into spectrum is CL6.
Comparative example 2
The NaOH solution 70mL that gets 1g ZSM-5,0.35mol/L places beaker, stirs 30min down in room temperature condition, changes in the closed reactor, handles 3.5h, filtration, washing in 50 ℃.ZSM-5 zeolite after the washing is placed beaker, and adding 0.5mol/L sulphuric acid soln 40mL stirs 40min down in room temperature condition, changes 80 ℃ of processing 3h in the water-bath over to, filters, washs, and places 110 ℃ of dry 12h of baking oven again, and the gained sample number into spectrum is CL7.
The pore structure character of the ZSM-5 modified zeolite sample that embodiment 1～5 and comparative example 1～2 are prepared is listed in table 1.
Embodiment 6
According to comparative example 1 method modified ZSM-5.Get the ZSM-5 zeolite 20g after the modification, 0.8mol/LNH
4NO
3200mL mixes in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again the gained solid matter is placed 110 ℃ of dry 12h of baking oven.Handle 4h in 550 ℃ then.Then carry out the high pressure compressing tablet, sieve is got 30～40 order samples toluene disproportionation process in micro-reaction equipment, and reaction conditions is: toluene air speed 3.0, temperature of reaction 440, reaction pressure 1.2MPa.The toluene turnover ratio is 20.25%, p-Xylol transformation efficiency 91.05%.
Embodiment 7
According to embodiment 1 method modified ZSM-5.Get the ZSM-520g after the modification, 0.8mol/L NH
4NO
3200mL mixes in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again the gained solid matter is placed 110 ℃ of dry 12h of baking oven.Handle 4h in 550 ℃ then.Then carry out the high pressure compressing tablet, sieve is got 30～40 order samples toluene disproportionation process in micro-reaction equipment, and reaction conditions is: toluene air speed 3.0, temperature of reaction 440, reaction pressure 1.2MPa.The toluene turnover ratio is 23.67%, p-Xylol transformation efficiency 96.25%.
The pore structure character of the related sample of table 1 embodiment
Claims (13)
1. the method for modifying of a ZSM-5 molecular sieve may further comprise the steps:
(1) get the ZSM-5 zeolite, the liquid-solid ratio adding alkaline solution according to 8～100mL/g stirs 0～60min under room temperature;
(2) mixture that step (1) is obtained places encloses container, according to the liquid-solid ratio adding lower molecular weight organic solvent of 0.5～10mL/g, handles 0.5～7h in 30～180 ℃;
(3) step (2) gained mixture is separated and wash;
(4) the ZSM-5 zeolite after the resulting alkaline purification of step (3) is mixed according to certain proportioning with acid solution, under room temperature, stir, then at 40～150 ℃ of following stir process 5～60min;
(5) products therefrom that obtains of step (4) is through separating, wash, be drying to obtain the ZSM-5 zeolite after the modification processing.
2. according to the described method of modifying of claim 1, it is characterized in that described alkaline solution is a kind of or several kinds the mixing solutions in NaOH, KOH, the LiOH aqueous solution.
3. according to the described method of modifying of claim 1, it is characterized in that the concentration of said alkaline solution is 0.1～7mol/L, the liquid-solid ratio of alkaline solution and ZSM-5 is 10～80mL/g.
4. according to the described method of modifying of claim 1, it is characterized in that the churning time described in the step (1) is 10～60min.
5. according to the described method of modifying of claim 1, it is characterized in that the temperature of alkaline purification is 40～120 ℃ described in the step (2), the treatment time is 2～4h.
6. according to the described method of modifying of claim 1, it is characterized in that the liquid-solid ratio of lower molecular weight organic solvent described in the step (2) and ZSM-5 zeolite is 0.5～10mL/g.
7. according to claim 1 or 6 described method of modifying, it is characterized in that described lower molecular weight organic solvent is meant that carbonatoms is 1～4 pure and mild ketone.
8. according to the described method of modifying of claim 7, it is characterized in that described lower molecular weight organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol and acetone.
9. according to the described method of modifying of claim 1, it is characterized in that the liquid-solid ratio of acid solution described in the step (4) and ZSM-5 is 20～100mL/g.
10. according to claim 1 or 9 described method of modifying, it is characterized in that described acid solution is selected from sulfuric acid, hydrochloric acid and salpeter solution, the concentration of acid solution is 0.1～3mol/L.
11., it is characterized in that the churning time described in the step (4) is 5～60min according to the described method of modifying of claim 1.
12., it is characterized in that acid-treated temperature is 40～150 ℃ described in the step (4) according to the described method of modifying of claim 1, the stir process time is 10～60min.
13., it is characterized in that step (5) gained ZSM-5 zeolite has following character: the XRD characteristic spectrogram with ZSM-5 zeolite according to the described method of modifying of claim 1; At N
2The measured aperture of adsorption-desorption exists mesoporous aperture to concentrate, and the most probable aperture is 3.5nm, and mesoporous specific surface area is 200～300m
2/ g, micropore specific area are 220～270m
2/ g.
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| CN103818925A (en) * | 2014-03-17 | 2014-05-28 | 中国石油大学(华东) | Method for preparing grade porous ZMS (Zeolite Socony Mobil)-5 molecular sieve by acid-base coupling |
| CN104229824A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Method for preparing gradational mesh ZSM-5 molecular sieve by virtue of acid-alkali coupling treatment |
| CN104399516A (en) * | 2014-12-11 | 2015-03-11 | 安徽工程大学 | Preparation method for photocatalyst for treating nitrophenol wastewater and treatment method for nitrophenol wastewater |
| CN104628011A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 modification treatment method |
| CN104974066A (en) * | 2014-04-01 | 2015-10-14 | 中国石油化工股份有限公司 | Preparation method of dimethyl sulfide |
| CN105712377A (en) * | 2014-12-01 | 2016-06-29 | 中国石油天然气股份有限公司 | Mesoporous ZSM-5 molecular sieve, and preparation method thereof |
| CN106395854A (en) * | 2016-08-26 | 2017-02-15 | 中国科学院上海硅酸盐研究所 | Preparation method of phosphorus modified multistage pore ZSM-5 zeolite |
| 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 |
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| CN104229824A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Method for preparing gradational mesh ZSM-5 molecular sieve by virtue of acid-alkali coupling treatment |
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| CN104399516B (en) * | 2014-12-11 | 2016-08-24 | 安徽工程大学 | The preparation method of photocatalyst of a kind for the treatment of of Nitrobenzene phenol waste water, the processing method of a kind of nitrophenol wastewater |
| CN104399516A (en) * | 2014-12-11 | 2015-03-11 | 安徽工程大学 | Preparation method for photocatalyst for treating nitrophenol wastewater and treatment method for nitrophenol wastewater |
| CN106395854A (en) * | 2016-08-26 | 2017-02-15 | 中国科学院上海硅酸盐研究所 | Preparation method of phosphorus modified multistage pore ZSM-5 zeolite |
| 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 |
| CN112295589A (en) * | 2019-08-02 | 2021-02-02 | 中国石油化工股份有限公司 | Catalyst for synthesizing durene and preparation method thereof |
| CN112295589B (en) * | 2019-08-02 | 2024-01-09 | 中国石油化工股份有限公司 | Catalyst for synthesizing durene and preparation method thereof |
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