CN106629769A - Preparation method of micron-sized HZSM-5 molecular sieve and application of micron-sized HZSM-5 molecular sieve - Google Patents
Preparation method of micron-sized HZSM-5 molecular sieve and application of micron-sized HZSM-5 molecular sieve Download PDFInfo
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Abstract
The invention discloses a micron-sized HZSM-5 molecular sieve catalyst. According to the micron-sized HZSM-5 molecular sieve catalyst disclosed by the invention, the micron-sized HZSM-5 molecular sieve is designed and synthesized by utilizing double-template, and thus, not only can acidity of the surface of a zeolite catalyst be modulated but also a diffusion path of a product can grow by increasing a particle size, and then, the goal of increasing para-selectivity is achieved. The invention further provides a preparation method of the micron-sized HZSM-5 molecular sieve and catalytic application of the micron-sized HZSM-5 molecular sieve. The micron-sized HZSM-5 molecular sieve catalyst provided by the invention is synthesized by a double-template one-step hydrothermal method, so that the preparation process is simple and convenient; when being applied to methyl bromide methylated methylbenzene to prepare paraxylene, the molecular sieve shows higher catalytic activity and selectivity during reaction; the catalyst shows the higher selectivity, which dues to fewer strong acid sites and a larger grain size; moreover, the catalyst has no corrosion on a fixed bed reactor, and generated hydrogen bromide tail gas is easy to recycle, so that the catalyst belongs to an environmentally friendly catalyst; and after being deactivated, the catalyst can be repeatedly used for more than once through simple roasting.
Description
【Technical field】
The present invention relates to Zeolite catalytic materials preparation and application technical field, relates in particular to a kind of micron order HZSM-5
The preparation method of molecular sieve and application.
【Background technology】
Paraxylene (PX) is a kind of important basic chemical industry raw material, numerous in polyester fiber, plastics, agricultural chemicals, medicine etc.
Chemical production field has extensive purposes, is widely used especially as the raw material of synthetic polyester fibers and plastics,
The demand of paraxylene also increasingly increases.At present, paraxylene is mainly by selective disproportionation of toluene, mixed xylenes absorption point
From or Crystallization Separation gained.But the production cost of these techniques is of a relatively high；In addition, in selective disproportionation of toluene technique, having
Substantial amounts of accessory substance benzene is generated.In recent years, there is higher paraxylene to select to prepare paraxylene with methanol alkylation toluene
Property and toluene utilization rate and enjoy the favor of people.But, methyl alcohol is typically prepared by synthesis gas route, need to be in HTHP ring
Synthesize in border, power consumption is big；And bromomethane is prepared by bromine oxidation of methane and avoids hyperbaric environment.Therefore, using bromomethane as methyl
Change reagent prepares paraxylene and has obvious superiority, and its synthesis path figure is as shown in Figure 1.
At present, a variety of zeolite based catalystses have been widely used in alkylation of toluene reaction.In these molecular sieves
In, because ZSM-5MFI topological structures have ten-ring duct, and pore size is suitable with paraxylene kinetic diameter, relative to
Ortho position and with meta dimethylbenzene, this duct is more beneficial for the diffusion of paraxylene, and ZSM-5 can be selected in toluene methylation process
Shape selectively produces paraxylene, and causes concern especially.But, it is raw due to strong or highly acid position in catalyst surface
Into paraxylene can rapid isomerization generate o-, m- dimethylbenzene, the selectivity for making paraxylene is remarkably decreased, so with not
Modified ZSM-5 is xylene concentration and the thermodynamic equilibrium value (p-xylene of generation in the toluene methylation process of catalyst
24%, m-xylene 51%, o-xylene 25%) closely.Therefore, higher para-selectivity is obtained, it is necessary to subtract
Less or eliminate strong in catalyst surface or highly acid position.Researchers develop the different ZSM-5 modification technologies of series to improve
The para-selectivity of dimethylbenzene, these methods impregnate including oxide, such as MgO, B2O3Or P2O5Deng；Surface silanization and pass through
Pre- coking to the process of organic carbonaceous material high temperature anaerobic etc..These methods can be obviously improved the contraposition in xylene isomer
It is selective, but catalyst preparation process is complicated, complex steps.
Additionally, the diffusion rate ratio of three kinds of isomers in ZSM-5 molecular sieve duct is in dimethylbenzene：It is (right：Between：
It is adjacent)=1000:1:10.The quickening of diffusion rate is conducive to improving its selectivity in dimethylbenzene.However, relatively short
In diffusion admittance, the diffusion advantage of paraxylene is not obvious.When catalyst size increase, when duct increases, paraxylene
Diffusion advantage will strengthen, so as to be conducive to its selective raising.
The crystallite dimension and pattern of zeolite catalyst has material impact to its catalytic performance.Organic formwork agent is in zeolite group
Structure directing can be played a part of during dress, interstitial space and balancing charge is filled up.It is micro- using double template design synthesis
Meter level HZSM-5, not only can modulation zeolite catalyst surface acidity, can also be by increasing particle size and build-up product
Diffusion path, and then reach the purpose for improving para-selectivity.Compared with the modified catalyst of tradition, this molecular sieve is in molecule
There is better performance in absorption and diffusion process.
【The content of the invention】
It is an object of the invention to provide a kind of preparation method of micron order HZSM-5 molecular sieves and application, and by the molecule
Sieve be applied to bromomethane methylate toluene prepare paraxylene reaction.The catalyst preparation is simple and easy to do, with higher activity
And selectivity.
The micron order HZSM-5 molecular sieve catalysts that the present invention is provided, using double template one-step synthesis method.
The synthetic method of the micron order HZSM-5 molecular sieve catalysts that the present invention is provided, comprises the steps of：
It is 100 by the mol ratio of material:[0.5～2]:[1～40]:[1～40]:[15～20]:[3800～4800]
Ratio takes respectively silicon source, silicon source, the first template, the second template, NaOH, water, is well mixed, by the colloidal sol being stirred
In being transferred to crystallizing kettle, static crystallization, cooling, centrifugation is washed to neutrality, is dried overnight, be subsequently placed in Muffle furnace by
Step is warming up to 400～700 DEG C, and molecular sieve Na-ZSM-5 is obtained after 1～5h of roasting；Carried out at 40～80 DEG C with ammonium nitrate solution
Ion exchange 3h, is repeated once, washing, is dried overnight, and is placed in Muffle furnace and is progressively warming up to 400～700 DEG C, 1～5h of roasting
After obtain molecular sieve HZSM-5；Wherein described silicon source and silicon source are respectively with oxide S iO2And Al2O3Meter.
In the preparation method of above-mentioned micron order HZSM-5 molecular sieve catalysts, SiO in the HZSM-5 molecular sieves2/Al2O3
For 50～200.
In the preparation method of above-mentioned micron order HZSM-5 molecular sieve catalysts, the silicon source is selected from Ludox or positive silicic acid
One or two in tetra-ethyl ester；Source of aluminium is at least one in aluminum sulfate, aluminum nitrate or aluminium chloride.
In the preparation method of above-mentioned micron order HZSM-5 molecular sieve catalysts, described the first template and the second template
It is to be respectively selected from TPAOH, tetraethyl ammonium hydroxide, 4-propyl bromide, triethylamine or triethanolamine not assimilate
Compound.
In the preparation method of above-mentioned micron order HZSM-5 molecular sieve catalysts, the condition of the static crystallization be 160～
200 DEG C of 24～72h of reaction.
It is still another object of the present invention to provide a kind of micron order HZSM-5 molecular sieves prepared by above-mentioned preparation method are urged
Agent catalysis bromomethane methylate toluene prepare paraxylene reaction in application.
Above-mentioned micron order HZSM-5 molecular sieve catalysts catalysis bromomethane methylate toluene prepare paraxylene reaction in,
Preparing the process conditions of paraxylene is：Nitrogen buffer gas, toluene air speed WHSV=2h-1, reactant bromomethane and toluene
Mol ratio is 1:2～2:1, reaction temperature is 400 DEG C.
The beneficial effects of the present invention is, the micron order HZSM-5 molecular sieve catalysts for being provided are by the step of double template one
Hydro-thermal method synthesizes, and preparation process is simple and easy to do.Organic formwork agent can play structure directing in zeolite assembling process, fill up hole
Gap space and the effect of balancing charge.Synthesizing micron-grade HZSM-5 is designed using double template, not only can modulation zeolite catalysis
The acidity on agent surface, also by increasing the diffusion path of particle size and build-up product, and then can reach raising para-selectivity
Purpose.When it is applied to catalytic reaction, catalysis activity is higher with selective.Catalyst shows higher selective attribution
In less strong acid site and larger crystallite dimension.Additionally, corrosion-free to fixed bed reactors, the hydrogen bromide tail gas of generation is easy
Reclaim, belong to environment-friendly catalyst.Can realize repeatedly using by simple roasting after catalyst inactivation.
【Brief Description Of Drawings】
Fig. 1 show using bromomethane the synthesis path figure that paraxylene is prepared as methylating reagent；
Fig. 2 show the HZSM-5 molecular sieve-4 As obtained by embodiment 1；
Fig. 3 show the HZSM-5 molecular sieve B obtained by embodiment 2；
Fig. 4 show the HZSM-5 molecular sieve C obtained by embodiment 3；
Fig. 5 show the NH of embodiment 1,2,3 and the HZSM-5 molecular sieve catalysts obtained by comparative example 1,23- TPD ratio
Relatively scheme.
【Specific embodiment】
Embodiment 1
By mol ratio SiO of material2:Al2O3:TPAOH:TEA:NaOH:H2O=100:0.67:30:10:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 24.402g TPAOHs (25wt.%),
1.012g triethylamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve-4 As of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 60%, and the para-selectivity of dimethylbenzene is 34%.
Embodiment 2
By mol ratio SiO of material2:Al2O3:TPAOH:TEA:NaOH:H2O=100:0.67:20:20:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 16.268g TPAOHs (25wt.%),
2.024g triethylamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve B of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 55%, and the para-selectivity of dimethylbenzene is 43%.
Embodiment 3
By mol ratio SiO of material2:Al2O3:TPAOH:TEA:NaOH:H2O=100:0.67:10:30:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 8.134g TPAOHs (25wt.%),
3.036g triethylamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve C of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 53%, and the para-selectivity of dimethylbenzene is 49%.
Embodiment 4
By mol ratio SiO of material2:Al2O3:TPAOH:TEOA:NaOH:H2O=100:0.67:20:20:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 16.268g TPAOHs (25wt.%),
2.984g triethanolamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, cooling, centrifugation, water
Neutrality is washed till, is dried overnight, be subsequently placed in Muffle furnace and be progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；
Ion exchange 3h is carried out at 80 DEG C with 1mol/L ammonium nitrate solutions, is repeated once, washed, be dried overnight, in being placed in Muffle furnace
550 DEG C are progressively warming up to, the HZSM-5 molecular sieve D of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 51%, and the para-selectivity of dimethylbenzene is 41%.
Embodiment 5
By mol ratio SiO of material2:Al2O3:TPABr:TEOA:NaOH:H2O=100:0.67:20:20:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 5.325g 4-propyl bromides, the ethanol of 2.984g tri-
Amine, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, and cooling, centrifugation is washed to neutrality, are dried
Overnight, it is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；Use 1mol/L nitric acid
Ammonium salt solution carries out ion exchange 3h at 80 DEG C, is repeated once, washing, is dried overnight, and is placed in Muffle furnace and is progressively warming up to 550
DEG C, the HZSM-5 molecular sieve E of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 52%, and the para-selectivity of dimethylbenzene is 38%.
Embodiment 6
By mol ratio SiO of material2:Al2O3:TPABr:TEA:NaOH:H2O=100:0.67:20:20:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 5.325g 4-propyl bromides, 2.024g triethylamines,
0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, cooling, and centrifugation is washed to neutrality, dried
At night, it is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；Use 1mol/L ammonium nitrate
Solution carries out ion exchange 3h at 80 DEG C, is repeated once, washing, is dried overnight, and is placed in Muffle furnace and is progressively warming up to 550
DEG C, the HZSM-5 molecular sieve F of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 51%, and the para-selectivity of dimethylbenzene is 42%.
Embodiment 7
By mol ratio SiO of material2:Al2O3:TEAOH:TEA:NaOH:H2O=100:0.67:20:20:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 11.781g tetraethyl ammonium hydroxides (25wt.%),
2.024g triethylamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve G of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 50%, and the para-selectivity of dimethylbenzene is 44%.
Embodiment 8
By mol ratio SiO of material2:Al2O3:TEAOH:TEOA:NaOH:H2O=100:0.67:20:20:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 11.781g tetraethyl ammonium hydroxides (25wt.%),
2.984g triethanolamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 24h, cooling, centrifugation, water
Neutrality is washed till, is dried overnight, be subsequently placed in Muffle furnace and be progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；
Ion exchange 3h is carried out at 80 DEG C with 1mol/L ammonium nitrate solutions, is repeated once, washed, be dried overnight, in being placed in Muffle furnace
550 DEG C are progressively warming up to, the HZSM-5 molecular sieve H of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 46%, and the para-selectivity of dimethylbenzene is 39%.
Embodiment 9
By mol ratio SiO of material2:Al2O3:TPAOH:TEA:NaOH:H2O=100:0.67:10:30:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 8.134g TPAOHs (25wt.%),
3.036g triethylamines, 0.660g NaOH and water, are well mixed, 160 DEG C of static crystallization 24h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve I of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 33%, and the para-selectivity of dimethylbenzene is 41%.
Embodiment 10
By mol ratio SiO of material2:Al2O3:TPAOH:TEA:NaOH:H2O=100:0.67:10:30:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 8.134g TPAOHs (25wt.%),
3.036g triethylamines, 0.660g NaOH and water, are well mixed, 200 DEG C of static crystallization 24h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve J of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 42%, and the para-selectivity of dimethylbenzene is 43%.
Embodiment 11
By mol ratio SiO of material2:Al2O3:TPAOH:TEA:NaOH:H2O=100:0.67:10:30:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 8.134g TPAOHs (25wt.%),
3.036g triethylamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 48h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve K of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 47%, and the para-selectivity of dimethylbenzene is 43%.
Embodiment 12
By mol ratio SiO of material2:Al2O3:TPAOH:TEA:NaOH:H2O=100:0.67:10:30:16.5:3800
Ratio, by 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 8.134g TPAOHs (25wt.%),
3.036g triethylamines, 0.660g NaOH and water, are well mixed, 180 DEG C of static crystallization 72h, cooling, centrifugation, washing
To neutral, it is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to 550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With
1mol/L ammonium nitrate solutions carry out ion exchange 3h at 80 DEG C, are repeated once, washing, be dried overnight, be placed in Muffle furnace by
Step is warming up to 550 DEG C, and the HZSM-5 molecular sieve L of Si/Al=75 are obtained after roasting 5h.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 48%, and the para-selectivity of dimethylbenzene is 45%.
Comparative example 1
By mol ratio SiO of material2:Al2O3:TPAOH:NaOH:H2O=100:0.67:40:16.5:3800 ratio,
By 20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 32.536g TPAOHs (25wt.%), 0.660g hydrogen
Sodium oxide molybdena and water, are well mixed, 180 DEG C of static crystallization 24h, and cooling, centrifugation is washed to neutrality, is dried overnight, then puts
550 DEG C are progressively warming up in Muffle furnace, molecular sieve Na-ZSM-5 is obtained after roasting 5h；With 1mol/L ammonium nitrate solutions at 80 DEG C
Under carry out ion exchange 3h, be repeated once, wash, be dried overnight, be placed in Muffle furnace and be progressively warming up to 550 DEG C, after roasting 5h
Obtain the HZSM-5 molecular sieve M of Si/Al=75.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 62%, and the para-selectivity of dimethylbenzene is 25%.
Comparative example 2
By mol ratio SiO of material2:Al2O3:TEA:NaOH:H2O=100:0.67:40:16.5:3800 ratio, will
20.03g Ludox (30wt.%), 0.446g aluminum sulfate, 4.048g triethylamines, 0.660g NaOH and water, are well mixed,
180 DEG C of static crystallization 24h, cooling, centrifugation is washed to neutrality, is dried overnight, is subsequently placed in Muffle furnace and is progressively warming up to
550 DEG C, molecular sieve Na-ZSM-5 is obtained after roasting 5h；Ion exchange 3h is carried out at 80 DEG C with 1mol/L ammonium nitrate solutions, weight
It is multiple once to wash, it is dried overnight, it is placed in Muffle furnace and is progressively warming up to 550 DEG C, the HZSM- of Si/Al=75 is obtained after roasting 5h
5 molecular sieve N.
Molecular sieve catalytic bromomethane methylate toluene prepare paraxylene reaction be in miniature fixed-bed quartz reactor
Carry out, take above-mentioned catalyst 1g, in nitrogen carrier gas flow velocity 10mL/min, toluene air speed WHSV=2h-1, reactant molar ratio n (bromines
Methane)：N (toluene)=2:1, reaction temperature is to react 1h, reactant liquor gas chromatographic analysis, first under 400 DEG C of operating condition
The conversion ratio of benzene is 32%, and the para-selectivity of dimethylbenzene is 54%.
The NH of catalyst obtained in comparative example 1,2 and the catalyst obtained by embodiment 1,2,33- TPD comparison diagrams such as accompanying drawing
Shown in 5, as a result show：Catalyst obtained by comparative example 1 has most highly acid positions, and obtained by comparative example 2
Catalyst only has two desorption peaks, there is no strong acid peak.When performance evaluation is carried out to prepared catalyst, comparative example 1
Obtained catalyst has minimum Selectivity for paraxylene, and there is catalyst obtained in comparative example 2 highest paraxylene to select
Selecting property, illustrating the highly acid position of catalyst makes the para-selectivity of dimethylbenzene substantially reduce.
Claims (7)
1. a kind of preparation method of micron order HZSM-5 molecular sieves, it is characterised in that comprise the steps of：
It is 100 by the mol ratio of material:[0.5～2]:[1～40]:[1～40]:[15～20]:The ratio of [3800～4800]
Silicon source, silicon source, the first template, the second template, NaOH, water are taken respectively, is well mixed, by the colloidal sol being stirred transfer
Into crystallizing kettle, static crystallization, cooling, centrifugation is washed to neutrality, is dried overnight, is subsequently placed in Muffle furnace and progressively rises
Temperature obtains molecular sieve Na-ZSM-5 to 400～700 DEG C after 1～5h of roasting；
Ion exchange 3h is carried out at 40～80 DEG C with ammonium nitrate solution, is repeated once, washed, be dried overnight, be placed in Muffle furnace
In be progressively warming up to 400～700 DEG C, molecular sieve HZSM-5 is obtained after 1～5h of roasting；
Wherein described silicon source and silicon source are respectively with oxide S iO2And Al2O3Meter.
2. the preparation method of micron order HZSM-5 molecular sieve catalysts according to claim 1, it is characterised in that described
SiO in HZSM-5 molecular sieves2/Al2O3For 50～200.
3. the preparation method of micron order HZSM-5 molecular sieve catalysts according to claim 1, it is characterised in that the silicon
Source is one or two in Ludox or tetraethyl orthosilicate；Source of aluminium is selected from aluminum sulfate, aluminum nitrate or chlorination
At least one in aluminium.
4. the preparation method of micron order HZSM-5 molecular sieve catalysts according to claim 1, it is characterised in that described
First template and the second template be respectively selected from TPAOH, tetraethyl ammonium hydroxide, 4-propyl bromide, three
Different compounds in ethamine or triethanolamine.
5. the preparation method of micron order HZSM-5 molecular sieve catalysts according to claim 1, it is characterised in that described quiet
The condition of state crystallization is to react 24～72h at 160～200 DEG C.
6. the micron order HZSM-5 molecular sieve catalysts that prepared by a kind of preparation method by described in claim 1 are in catalysis bromomethane
The toluene that methylates prepares the application in paraxylene reaction.
7. the micron order HZSM-5 molecular sieve catalysts described in claim 6 methylate toluene preparation to diformazan in catalysis bromomethane
Application in benzene reaction, it is characterised in that preparing the process conditions of paraxylene is：Nitrogen buffer gas, toluene air speed WHSV
=2h-1, reactant bromomethane is 1 with the mol ratio of toluene:2～2:1, reaction temperature is 400 DEG C.
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| CN112387303A (en) * | 2019-08-14 | 2021-02-23 | 国家能源投资集团有限责任公司 | Modified ZSM-5 molecular sieve, preparation method and application thereof, catalyst and application thereof |
| CN112473726A (en) * | 2019-09-11 | 2021-03-12 | 国家能源投资集团有限责任公司 | Composite ZSM-5 molecular sieve, preparation method thereof, catalyst and application thereof |
| CN115475653A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Benzene and ethanol gas phase alkylation catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112387303A (en) * | 2019-08-14 | 2021-02-23 | 国家能源投资集团有限责任公司 | Modified ZSM-5 molecular sieve, preparation method and application thereof, catalyst and application thereof |
| CN112387303B (en) * | 2019-08-14 | 2024-04-26 | 国家能源投资集团有限责任公司 | Modified ZSM-5 molecular sieve, preparation method and application thereof, and catalyst and application thereof |
| CN112473726A (en) * | 2019-09-11 | 2021-03-12 | 国家能源投资集团有限责任公司 | Composite ZSM-5 molecular sieve, preparation method thereof, catalyst and application thereof |
| CN112473726B (en) * | 2019-09-11 | 2022-01-28 | 国家能源投资集团有限责任公司 | Composite ZSM-5 molecular sieve, preparation method thereof, catalyst and application thereof |
| CN112142066A (en) * | 2020-11-06 | 2020-12-29 | 四川润和催化新材料股份有限公司 | Method for synthesizing ZSM-48 molecular sieve by using double templates |
| CN112142066B (en) * | 2020-11-06 | 2021-06-22 | 润和催化剂股份有限公司 | Method for synthesizing ZSM-48 molecular sieve by using double templates |
| CN115475653A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Benzene and ethanol gas phase alkylation catalyst and preparation method and application thereof |
| CN115475653B (en) * | 2021-06-16 | 2024-03-29 | 中国石油化工股份有限公司 | Benzene and ethanol gas phase alkylation catalyst and preparation method and application thereof |
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