CN102190317B - ZSM-5 sieve material used for aromatic hydrocarbons alkylation reaction and preparation method thereof - Google Patents
ZSM-5 sieve material used for aromatic hydrocarbons alkylation reaction and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a ZSM-5 sieve material used for an aromatic hydrocarbons alkylation reaction and a preparation method thereof. The invention is mainly used to solve the problems in the prior art that the recovery rate of a fine grain zeolite molecular sieve is low and the stability of an original sieve material used for the aromatic hydrocarbons alkylation reaction is not ideal. According to the invention, the problems are well solved by the technical scheme of the ZSM-5 sieve material and its preparation method. The ZSM-5 sieve material is characterized in that the pore volume is larger than 30m<2>/g, the molar ratio of SiO2 and Al2O3 is between 15 to 800, the size of zeolite particles is between 200 to 2000nm, the sieve material is agglomerated from base nanometer zeolite particles having a size between 10 to 80nm, the diffraction peak (111), (501) and (151) suffer from severe attenuation and even disappear and a width phenomenon happens to the diffraction peak (011) and (051). The ZSM-5 sieve material can be applied to the industrial production of alkylation of aromatic hydrocarbons such as benzene and toluene.
Description
Technical field
The present invention relates to a kind of ZSM-5 molecular sieve material for alkylation reaction of arene and preparation method thereof.
Background technology
P-Xylol (PX) is important chemical intermediate, in fields such as trevira, medicine, agricultural chemicals, dye well solvents extremely widely purposes is arranged all.Because the PX demand is growing, directly from reformate and pyrolysis gasoline extracting with separate PX and far can not satisfy the demands.The method of industrial production p-Xylol mainly contains toluene and C
9Aromatic disproportion and transalkylation, xylol isomerization and selective disproportionation of toluene.Therefore, benzene and toluene are changed into to greatest extent the high added value p-Xylol of market demand, be important research direction in the petrochemical technology always.Toluene or benzene and methanol shape selective alkylation technique are then produced the low benzene that even do not produce of benzene amount, and have therefore improved the utilization ratio of methylbenzene raw material, adapt to especially the present situation of Present Domestic benzene glut the market.Yet because reaction system has been introduced methyl alcohol, methyl alcohol the coking reaction very easily occurs under alkylation reaction condition and causes catalyst deactivation, this problem is the difficult problem of restriction alkylation of toluene methanol technical development always.
ZSM-5 zeolite has the staggered pore passage structure of two-dimentional ten-ring,, has obtained using very widely in the important petrochemical process such as catalytic cracking, alkylation, disproportionation and xylene isomerization from Mobil company since the exploitation seventies in last century.By regulating synthesis condition, its crystalline size also can be regulated in the larger context, from tens nanometer to tens microns.The zeolite grain surfaces externally and internally all comprises the solid acid position, and along with the zeolite grain size variation, the hydroxyl acidic site of outside surface accounts for the 3-5% of total acidic position usually.Nano zeolite refers to the zeolite of grain size between 1nm～100nm.Because crystal grain is minimum, the specific surface area of nano zeolite especially outer surface area obviously increases, the surface atom number sharply increases with the ratio of volume atomicity, shorten in the duct, exposing the aperture increases, thereby make nano zeolite have higher reactive behavior and surface energy, be particularly conducive to the catalyzed reaction that needs reactant and product rapid diffusion, improve transformation efficiency and suppress inactivation.Therefore, according to the characteristics of alkylation reaction of arene, exploitation is beneficial to diffusion, effectively prevents the zeolite molecular sieve material of carbon deposit, is the key that industrializeding catalyst is succeeded in developing.
Can be divided into two classes by small-particle ZSM-5 zeolite Zeolite synthesis system difference, a class can be described as without the sodium synthesis method, and another kind of then is to have sodium synthetic.Generally take TPAOH (TPAOH) as alkali source, tetraethoxy (TEOS) is the silicon source without the sodium synthesis method, and synthesis temperature and crystallization time change according to the difference of reaction mixture proportioning.Have the sodium synthesis method can use template relatively inexpensive, environmental protection, synthetic cost is lower, has industrial applications and is worth, and has also reported multiple preparation method in document and the patent.The people such as Yamamura take silicon sol as the silicon source, aluminum nitrate as the aluminium source, sodium hydroxide as alkali source, 4-propyl bromide (TPABr) as template, under 433K, obtain the ZSM-5 zeolite aggregate (Zeolites of 30～50nm through dynamic crystallization, 1994,14,643.).Guo Hongchen etc. are take n-Butyl Amine 99 as template, water glass is the silicon source, Tai-Ace S 150 is the aluminium source, sodium hydroxide is that alkali source has been prepared the nano-ZSM-5 zeolite molecular sieve, discovery is under suitable NaCl consumption condition, crystallization is more than 4 days under the cold condition, and the I of crystal grain reaches 40nm (CN 1699173A).Wang Jun etc. have also reported the preparation method (CN 1958453A) of a kind of synthesizing small crystal grain ZSM-5-5, and by regulate the pH value of the mixed solution of silicon source and deionized water with acid solution, Hydrothermal Synthesis obtains particle diameter between the small-grain ZSM-5 of 100～200nm.Hu Jinxian etc. then prepare the sial directed agents take organic amine as template, then join in the Zeolite synthesis system, hydrothermal crystallizing can get the ZSM-5 molecular sieve (CN1303816A) of median size 100nm in 65～75 hours, but the scope of its silica alumina ratio can only be controlled between 20～100, can obtain quartzy phase impurity under higher silica alumina ratio condition.In addition, the people such as Shiralkar find, the crystal seed that in synthetic system, adds KF and 1%wt～10%wt all the crystal grain of ZSM-5 is reduced (Zeolites, 1991,11:511).Yet, the particle that the little crystal grain zeolite of these method preparations all is high dispersing, this just causes the rate of recovery of filtration, washing and exchange process lower; Simultaneous reactions thing and product molecule are difficult for diffusion in the macrobead zeolite, this makes its rapid deactivation in alkylation reaction of arene, and stability is not good.
Summary of the invention
One of technical problem to be solved by this invention is that the particulate zeolite molecular sieve rate of recovery that exists in the prior art is low, and the not good problem of stability that is used for alkylation reaction of arene provides a kind of new ZSM-5 molecular sieve material that is used for alkylation reaction of arene and preparation method thereof.This kind ZSM-5 zeolite molecular screen material is used for the alkylation catalyst of benzene and toluene, has advantages of that the ZSM-5 zeolite molecular sieve rate of recovery is high, catalyst activity is stable good.Two of technical problem to be solved by this invention provides a kind of new ZSM-5 molecular sieve material preparation method corresponding with one of technical solution problem.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ZSM-5 molecular sieve material for alkylation reaction of arene has following characteristics:
A) total specific surface area is greater than 300m
2/ g, middle pore specific surface area is greater than 30m
2/ g;
B) SiO
2/ Al
2O
3Mol ratio between 15～800;
C) the zeolite granular size is between 200～2000nm, and reunited by the basic Colloidal zeolites of 10～80nm and to form;
D) its (111), (501) and (151) diffraction peak seriously weaken even disappear, (011) and (051) diffraction peak generation broadening phenomenon.
In the technique scheme, total specific surface area preferred version is greater than 350m
2/ g, middle pore specific surface area is greater than 45m
2/ g.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of the ZSM-5 molecular sieve for alkylation reaction of arene, take water glass, silicon sol or solid silica flour as the silicon source, aluminium salt or sodium aluminate are the aluminium source, with ethanol, acetone, ammoniacal liquor, ethamine, n-Butyl Amine 99,4-propyl bromide or TPAOH as template R1; The mole proportioning of crystallization system is 5～30 Na
2O: Al
2O
3: 15～800 SiO
2: 0～20 Rl
2O: 10～800 H
2O, crystallization temperature are 80～200 ℃, and crystallization time is 2～80 hours, makes ZSM-5 zeolite; In mother liquor, add with SiO before the crystallization
2The zeolite precursor liquid solution of cubage 0.2～10%, the zeolite precursor body is 0～2 Al by the feed molar proportioning
2O
3: 100SiO
2: 1～10 R2
2O: 10～100 H
2The mixture of O gets at 30～140 ℃ of lower hydro-thermal reaction 4～150h, and ethamine, n-Butyl Amine 99,4-propyl bromide or TPAOH are as template R2.
In the technique scheme, the mole proportion optimization scope of crystallization system is (5～30) Na
2O: Al
2O
3: (20～600) SiO
2: (1～12) Rl
2O: (10～800) H
2O, the add-on of zeolite precursor body is with SiO
2Cubage is 1～6% of mother liquor.Template R1 preferred version is selected from ethanol, acetone, ammoniacal liquor, ethamine, n-Butyl Amine 99 or 4-propyl bromide.Aluminium salt preferred version is selected from Tai-Ace S 150, aluminum nitrate or Wickenol CPS 325.Template R2 preferred version is selected from n-Butyl Amine 99,4-propyl bromide or TPAOH.
The present invention in the crystallization system because the zeolite precursor body that to have added secondary zeolite structured unit be state of aggregation, this has not only brought into play good guide effect in the secondary crystallization process of ZSM-5 zeolite, and so that the basic Colloidal zeolites that forms in the crystallization process has been gathered into the micron particles of being convenient to separate naturally, the rate of recovery is high.Take the aromatic alkylation catalysts of this kind molecular sieve as the basis preparation, the diffusion admittance of nano particle is very short, and has abundant step mesopore duct, is very suitable for the alkylated reaction of benzene and toluene, the catalyst activity good stability.Catalyzer with the preparation of this kind zeolite molecular sieve, the alkylated reaction that is used for benzene and toluene, benzene with 80～100% and toluene and 90～100% methyl alcohol are as raw material, temperature of reaction is between 280～450 ℃, catalyst stability significantly improves, satisfy the requirement of industrializeding catalyst, obtained preferably technique effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Prepare in advance the zeolite precursor body: take ethamine as template, with silicon sol (40% weightaqueous solution) and sodium aluminate respectively as silicon source and aluminium source, according to Al
2O
3: 100SiO
2: 6CH
3CH
2NH
2: 80H
2The mol ratio preparating mixture of O, and take the pH value of sodium hydroxide regulation system as 12.5, then hydro-thermal reaction 24 hours under 170 ℃ of temperature condition.
(contain 25.3% weight SiO with water glass respectively
2) and Tai-Ace S 150 as silicon source and aluminium source, with 4-propyl bromide (R) as template, with the pH value of vitriol oil regulation system, according to 12Na
2O: Al
2O
3: 120SiO
2: 13R
2O: 650H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 5% weight in the crystallization mother liquor, static crystallization 48h under 180 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and just (111), (501) and (151) diffraction peak seriously weaken (011) and (051) diffraction peak generation broadening phenomenon.It is 380.2m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 45.6m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 30～50nm is assembled the approximately 1100nm size form.
[embodiment 2]
Prepare in advance the zeolite precursor body: take n-Butyl Amine 99 as template, with silica flour and sodium aluminate respectively as silicon source and aluminium source, according to Al
2O
3: 200 SiO
2: 4CH
3CH
2CH
2CH
2NH
2: 350H
2The mol ratio preparating mixture of O, and take the pH value of sodium hydroxide regulation system as 12.5, then hydro-thermal reaction 36 hours under 175 ℃ of temperature condition.
(contain 40% weight SiO with silicon sol respectively
2) and aluminum nitrate as silicon source and aluminium source, with TPAOH (R) as template, with the pH value of sodium hydroxide regulation system, according to 10Na
2O: Al
2O
3: 180SiO
2: 3R
2O: 400H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 6% weight in the crystallization mother liquor, static crystallization 36h under 160 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and just (111), (501) and (151) diffraction peak seriously weaken (011) and (051) diffraction peak generation broadening phenomenon.It is 396.5m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 48.3m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 30～50nm is assembled the approximately 1500nm size form.
[embodiment 3]
Prepare in advance the zeolite precursor body: take TPAOH as template (R), with tetraethoxy as the silicon source, according to 3SiO
2: 2R
2O: 50H
2The mol ratio preparating mixture of O, and take the pH value of ammoniacal liquor regulation system as 12.5, then hydro-thermal reaction 12 hours under 120 ℃ of temperature condition.
(contain 40% weight SiO with silicon sol respectively
2) and sodium aluminate as silicon source and aluminium source, with 4-propyl bromide (R) as template, with the pH value of sodium hydroxide regulation system, according to 6Na
2O: Al
2O
3: 260SiO
2: 12R
2O: 360H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 1% weight in the crystallization mother liquor, static crystallization 96h under 130 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and just (111), (501) and (151) diffraction peak disappear, and serious broadening phenomenon occurs (011) and (051) diffraction peak.It is 469.8m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 67.3m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 10～30nm is assembled the approximately 400nm size form.
[embodiment 4]
Prepare in advance the zeolite precursor body: take TPAOH as template (R), with tetraethoxy as the silicon source, according to 3SiO
2: 2R
2O: 50H
2The mol ratio preparating mixture of O, and take the pH value of ammoniacal liquor regulation system as 12.5, then hydro-thermal reaction 96 hours under 60 ℃ of temperature condition.
(contain 40% weight SiO with silicon sol respectively
2) and sodium aluminate as silicon source and aluminium source, with 4-propyl bromide (R) as template, with the pH value of sodium hydroxide regulation system, according to 5.5Na
2O: Al
2O
3: 260SiO
2: 12R
2O: 360H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 3% weight in the crystallization mother liquor, static crystallization 4h under 130 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and just (111), (501) and (151) diffraction peak disappear, and serious broadening phenomenon occurs (011) and (051) diffraction peak.It is 489.2m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 73.6m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 10～30nm is assembled the approximately 300nm size form.
[embodiment 5]
Prepare in advance the zeolite precursor body: take 4-propyl bromide as template (R), with tetraethoxy as the silicon source, with sodium aluminate as the aluminium source, according to Al
2O
3: 120SiO
2: 50R
2O: 780H
2The mol ratio preparating mixture of O, and take the pH value of sodium hydroxide regulation system as 12.8, then hydro-thermal reaction 18 hours under 140 ℃ of temperature condition.
(contain 25.3% weight SiO with water glass respectively
2) and Tai-Ace S 150 as silicon source and aluminium source, with ethamine as template, with the pH value of vitriol oil regulation system, according to 8Na
2O: Al
2O
3: 80SiO
2: 19R
2O: 500H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 2% weight in the crystallization mother liquor, static crystallization 48h under 180 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, just (111), the reduction of (501) and (151) diffraction peak, (011) and (051) diffraction peak generation broadening phenomenon.It is 378.3m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 35.2m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 50～80nm is assembled the approximately 1900nm size form.
[embodiment 6]
Prepare in advance the zeolite precursor body: take 4-propyl bromide as template (R), with tetraethoxy as the silicon source, with sodium aluminate as the aluminium source, according to Al
2O
3: 200SiO
2: 50R
2O: 780H
2The mol ratio preparating mixture of O, and take the pH value of sodium hydroxide regulation system as 12.8, then hydro-thermal reaction 24 hours under 100 ℃ of temperature condition.
Respectively with silica flour and aluminum oxide as silicon source and aluminium source, with n-Butyl Amine 99 (R) as template, with the pH value of sodium hydroxide regulation system, according to 17Na
2O: Al
2O
3: 150SiO
2: 19R
2O: 300H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 4% weight in the crystallization mother liquor, static crystallization 48h under 160 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, just (111), the reduction of (501) and (151) diffraction peak, (011) and (051) diffraction peak generation broadening phenomenon.It is 323.6m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 32.8m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 50～60nm is assembled the approximately 800nm size form.
[embodiment 7]
Prepare the zeolite precursor body according to method among the embodiment 6.
(contain 25.3% weight SiO with water glass respectively
2) and aluminum nitrate as silicon source and aluminium source, with ammoniacal liquor (R) as template, with the pH value of vitriol oil regulation system, according to 40Na
2O: Al
2O
3: 500SiO
2: 80R
2O: 2000H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 2% weight in the crystallization mother liquor, and static crystallization is 6 hours under 180 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and just (111), the reduction of (501) and (151) diffraction peak is (O11) with (051) diffraction peak generation broadening phenomenon.It is 378.3m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 35.2m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 50～80nm is assembled the approximately 1900nm size form.
[embodiment 8]
Prepare the zeolite precursor body according to method among the embodiment 4.
(contain 40% weight SiO with silicon sol respectively
2) and sodium aluminate as silicon source and aluminium source, with ethanol (R) as template, with the pH value of sodium hydroxide regulation system, according to 24Na
2O: Al
2O
3: 50SiO
2: 7R
2O: 1200H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 3% weight in the crystallization mother liquor, and static crystallization is 24 hours under 190 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and just (111), (501) and (151) diffraction peak disappear, and serious broadening phenomenon occurs (011) and (051) diffraction peak.It is 368.9m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 45.3m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 20～30nm is assembled the approximately 700nm size form.
[embodiment 9]
Prepare the zeolite precursor body according to method among the embodiment 3.
(contain 25.3% weight SiO with water glass respectively
2) and Tai-Ace S 150 as silicon source and aluminium source, with acetone (R) as template, with the pH value of vitriol oil regulation system, according to 37Na
2O: 4Al
2O
3: 5008iO
2: 80R
2O: 1600H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 2% weight in the crystallization mother liquor, static crystallization 24h under 160 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, just (111), the reduction of (501) and (151) diffraction peak, (011) and (051) diffraction peak generation broadening phenomenon.It is 336.5m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 34.6m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 60～80nm is assembled the approximately 1500nm size form.
[embodiment 10～12]
Prepare the zeolite precursor body according to method among the embodiment 3.
(contain 40% weight SiO with silicon sol respectively
2) and sodium aluminate as silicon source and aluminium source, with TPAOH (R) as template, with the pH value of sodium hydroxide regulation system, according to 10Na
2O: Al
2O
3: 15SiO
2: 2R
2O: 450H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 3% weight in the crystallization mother liquor, static crystallization 2h, 4h and 8h under 160 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and just (111), (501) and (151) diffraction peak disappear, and serious broadening phenomenon occurs (011) and (051) diffraction peak.It is 368.9m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 45.3m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 10～30nm is assembled the approximately 400nm size form.
[embodiment 13]
Prepare the zeolite precursor body according to method among the embodiment 3.
(contain 40% weight SiO with silicon sol
2) as the silicon source, with TPAOH (R) as template, with the pH value of sodium hydroxide regulation system, according to 12Na
2O: 15SiO
2: 2R
2O: 600H
2The mole proportioning of O preparation crystallization mother liquor adds the zeolite precursor body of 3% weight in the crystallization mother liquor, and static crystallization 16h prepares pure silicon ZSM-5 under 160 ℃ of conditions.Product X RD collection of illustrative plates shows that it is the ZSM-5 structure, and serious broadening phenomenon occurs (011) and (051) diffraction peak.It is 368.9m that its total specific surface area is measured in physical adsorption
2/ g, middle pore specific surface area are 45.3m
2/ g.The SEM Electronic Speculum shows that product is the irregular sphere that the nanoparticle of 20～30nm is assembled the approximately 700nm size form.
[embodiment 14]
Among the embodiment 6 gained ZSM-5 molecular sieve and aluminum oxide according to 5: 5 ratio kneading after extruded moulding, oven dry, roasting namely gets alkylation catalyst.Under hydro condition, in fixed-bed reactor, carry out the alkylation properties of toluene and methyl alcohol and investigate.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down all 3 millimeters granulated glass spherees of filling Φ play air-flow and distribute and supporting role, the centre 20g alkylation catalyst of packing into.The alkylated reaction of toluene and methyl alcohol occurs at catalyzer, and toluene level 95.2% in the aroamtic hydrocarbon raw material, and methanol purity is 98%, the mol ratio of toluene and methyl alcohol is 2.5,400 ℃ of temperature of reaction, pressure 0.5MPa, weight hourly space velocity (WHSV) is 4, and hydrogen and aromatic hydrocarbons mol ratio are 3.Reactivity worth is as follows: toluene average conversion 28.1%, use ratio of methanol are 65.6%, and obvious inactivation did not occur in 800 hours in catalyzer steady running.
[embodiment 15]
Among the embodiment 4 gained ZSM-5 molecular sieve and aluminum oxide according to 6: 4 ratio kneading after extruded moulding, oven dry, roasting namely gets alkylation catalyst.Under hydro condition, in fixed-bed reactor, carry out the alkylation properties of benzene and methyl alcohol and investigate.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down all 3 millimeters granulated glass spherees of filling Φ play air-flow and distribute and supporting role, the centre 20g alkylation catalyst of packing into.The alkylated reaction of benzene and methyl alcohol occurs at catalyzer, benzene content 98.5% in the aroamtic hydrocarbon raw material, methanol purity is 98%, the mol ratio of benzene and methyl alcohol is 3.5,380 ℃ of temperature of reaction, pressure 0.2MPa, weight hourly space velocity (WHSV) is 2.5.Reactivity worth is as follows: benzene average conversion 16.8%, use ratio of methanol are 63.5%, and obvious inactivation did not occur in 500 hours in catalyzer steady running.
Claims (2)
1. ZSM-5 molecular sieve material that is used for alkylation reaction of arene has following characteristics:
A) physical adsorption is measured total specific surface area greater than 300m
2/ g, middle pore specific surface area is greater than 30m
2/ g;
B) SiO
2/ Al
2O
3Mol ratio between 15～800;
C) the zeolite granular size is between 200～2000nm, and reunited by the basic Colloidal zeolites of 10～80nm and to form;
D) its (111), (501) and (151) diffraction peak disappear (011) and (051) diffraction peak generation broadening phenomenon.
2. the ZSM-5 molecular sieve material for alkylation reaction of arene according to claim 1 is characterized in that total specific surface area is greater than 350m
2/ g, middle pore specific surface area is greater than 45m
2/ g.
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| CN102826568B (en) * | 2012-09-26 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | The preparation method of nanocrystalline ZSM-5 zeolite cluster and nanocrystalline ZSM-5 zeolite cluster obtained by this method |
| SG11201502644SA (en) | 2012-10-05 | 2015-05-28 | Basf Se | Process for the production of a zeolitic material employing elemental precursors |
| CN103007985B (en) * | 2012-12-20 | 2014-09-24 | 清华大学 | Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof |
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| CN104724720B (en) * | 2015-03-18 | 2017-08-15 | 宁夏大学 | A kind of synthetic method of the molecular sieves of HZSM 5 |
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| CN1187462A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN1699173A (en) * | 2005-06-14 | 2005-11-23 | 大连理工大学 | Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio |
| CN1935652A (en) * | 2006-10-19 | 2007-03-28 | 华东师范大学 | Method for synthesizing ZSM-5 molecular sieve |
| CN101190418A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Method for preparing fine grain ZSM-5/mordenite composite molecular sieve |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187462A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN1699173A (en) * | 2005-06-14 | 2005-11-23 | 大连理工大学 | Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio |
| CN1935652A (en) * | 2006-10-19 | 2007-03-28 | 华东师范大学 | Method for synthesizing ZSM-5 molecular sieve |
| CN101190418A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Method for preparing fine grain ZSM-5/mordenite composite molecular sieve |
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