CN109772437A - A kind of method and application that ZSM-5 molecular sieve surface is modified - Google Patents
A kind of method and application that ZSM-5 molecular sieve surface is modified Download PDFInfo
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Abstract
A kind of ZSM-5 molecular sieve surface modifying method, it comprises the steps of: and weighs the surface modifier organic matter containing C, N, S element, be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, the volume ratio of water and ethyl alcohol is 1:4 in mixed liquor, surface modifier is obtained, concentration is 0.1 ~ 1.0 mol/L；Surface modifier is mixed with ZSM-5 molecular sieve again, the volume ratio of surface modifier and ZSM-5 molecular sieve is 1:1；After stirring evenly, drying, by obtained solid in the processing of atmosphere of inert gases high temperature, makes C, N, S element deposition in molecular sieve surface, obtain the modified ZSM-5 molecular sieve in surface；The acidity that catalyst surface can effectively be adjusted improves the acid site B of catalyst surface and the ratio in the acid site L, and gained catalyst has excellent catalytic properties, and the selectivity of dimethylbenzene is also higher in product.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of method and application that ZSM-5 molecular sieve surface is modified.
Background technique
Aromatic hydrocarbons is the important basic material of organic chemical industry, in chemical fields such as production plastics, synthetic fibers and synthetic rubber
With extremely extensive purposes.Currently, aromatic hydrocarbons is mainly derived from petroleum catalytic reforming, naphtha pyrolysis, coal tar hydrogenating and urges
Change the techniques such as cracking.However, with the rapid hair of the chemical industry such as the shortage of world petroleum resource and dyestuff, medicine, plastics
Exhibition causes worldwide aromatic production to be unable to satisfy demand, aromatic hydrocarbons price it is high long not under.And demand and price to aromatic hydrocarbons
Constantly increase the development for stimulating new aromatics production technique, converting methanol into aromatic hydrocarbons (MTA) will be a kind of very attractive
Synthesis aromatic hydrocarbons approach.
Methanol is a kind of more clean energy, can be obtained from coal, coke, shale gas and biomass etc. extensively resource.By
It is quite abundant in coal resources in China, it is increasingly mature by the technique of Material synthesis methanol of coal, lead to China's methanol production capacity
It is serious superfluous.Although methanol accounting in the consumption in the fields such as production formaldehyde, low-carbon alkene, synthetic rubber, fuel is larger, this
A little fields general consumption amount is still smaller.Methanol must constantly be widened in the application in other fields, find one for methanol application
Explosive growth point, just can effectively solve methanol problem of excess production capacity in this way.Therefore, aromatization of methanol technique will become China
Aromatics production and the approach for solving methanol problem of excess production capacity, are effectively reduced aromatic hydrocarbon product to the dependence of fossil resource.
ZSM-5 molecular sieve is a kind of micropore alumino-silicate, has MFI topological structure.It acid, unique is selected since its is adjustable
Shape, good hydrothermal stability and uniform rule 3 tie up the high-quality performances such as pore structure, are that MTA reaction generally acknowledged at present is most suitable
Molecular sieve catalyst.
Methanol conversion on ZSM-5 molecular sieve catalyst is typical acid catalysis process, and catalyst surface carbon distribution is
The main reason for catalyst inactivation.Therefore, improve the carbon accumulation resisting ability of catalyst, be current MTA catalysis to improve its stability
The emphasis of agent research.In MTA reaction process, by reducing the acidity of the outer surface ZSM-5, coke laydown rate can be effectively delayed
And improve catalytic stability.In addition, the acid site B of catalyst surface and the ratio in the acid site L also have a significant impact to reaction, B/
L ratio is higher, and it is also more advantageous to generate aromatic hydrocarbons to methanol oxidation.Currently, passing through the post-processing approach modified ZSM-5s such as acid, alkali, hydro-thermal
Molecular sieve can improve the anti-carbon performance of molecular sieve.These methods not only can change the outer surface of catalyst acid distribution and
Acid amount, can also change the properties such as the pore structure of molecular sieve.But acid, alkali can cause certain break to molecular sieve crystalline structure
It is bad, the skeleton structure of ZSM-5 molecular sieve can be also destroyed, so that total acid content and acid strength seriously reduce, to a certain extent
The activity for influencing catalyst causes to reduce the selectivity of product, meanwhile, acid, alkali treatment method have waste water generation.
Summary of the invention
Present invention aim to address above-mentioned problems of the prior art, provides and improve comprehensive performance, and do not break
A kind of ZSM-5 molecular sieve surface modifying method of the skeleton structure of bad ZSM-5 molecular sieve and application.
The present invention is implemented as follows:
It comprises the steps of: and weighs the surface modifier organic matter containing C, N, S element, be dissolved in the mixed of 1000 milliliters of water and ethyl alcohol
It closes in liquid, the volume ratio of water and ethyl alcohol is 1:4 in mixed liquor, obtains surface modifier, and concentration is 0.1 ~ 1.0 mol/L；Again will
Surface modifier is mixed with ZSM-5 molecular sieve, and the volume ratio of surface modifier and ZSM-5 molecular sieve is 1:1；It stirs evenly, do
After dry, by obtained solid in the processing of atmosphere of inert gases high temperature, make C, N, S element deposition in molecular sieve surface, obtain surface
Modified ZSM-5 molecular sieve；
The surface modifier organic matter containing C, N, S element is glucose, urea, rhodamine B, thiophene or trimerization as described above
One of cyanamide；
The time stirred after addition ZSM-5 molecular sieve as described above is 3 ~ 8 h, and whipping temp is 60 ~ 100 DEG C；Drying time
For 8 ~ 12 h, drying temperature is 60 ~ 100 DEG C；The high-temperature process time is 4 ~ 8 h, and high-temperature process temperature is 500 ~ 700 DEG C；
Inert gas as described above is nitrogen or helium or argon gas.
The present invention has the advantages that first surface modifier and ZSM-5 molecular sieve are stirred evenly, in ZSM-5 molecular sieve table
Organic molecule is adsorbed on face, after dry, then through atmosphere of inert gases high-temperature process, makes C, N, S element deposition in ZSM-5 molecule
Surface is sieved, and then realizes the modification to ZSM-5 molecular sieve surface, the preparation method is easy to operate, can effectively adjust catalyst table
The acidity in face, and the acid site B of catalyst surface and the ratio in the acid site L can be improved, gained catalyst has excellent catalysis
Performance, the selectivity of dimethylbenzene is also higher in product.
1, modified by C, N, S to ZSM-5 molecular sieve surface, the acidity of energy Effective Regulation molecular sieve surface is shown in Table 1；
2, the acid amount on ZSM-5 molecular sieve surface can be adjusted by changing the concentration of modification liquid, be shown in Table 1；
3, after modified, the ratio of the B acid of molecular sieve surface and L acid can significantly improve, and be shown in Table the raising of 1, B/L ratio, more have
Aromatic hydrocarbons is generated conducive to catalysis methanol aromatisation.
Specific embodiment
Present invention combination following instance is further described:
Embodiment 1:
Compound concentration is the glucose solution of 0.1 mol/L: taking glucose to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixes
Closing the volume ratio of water and ethyl alcohol in liquid is 1:4, and obtaining concentration is 0.1mol/L surface modifier；
It is again that isometric SiO is added into solution under 0.1 mol/L surface modifier stirring condition by 10 mL concentration2/Al2O3
=46 ZSM-5 molecular sieve, is put into oil bath pan after mixing evenly, and 8 h are stirred at 60 DEG C, is put into air dry oven 60 DEG C
Dry 12 h, then in nitrogen atmosphere at 550 DEG C 5 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.Then
It is applied to catalysis methanol aromatization.
Embodiment 2:
Compound concentration is the glucose solution of 0.2 mol/L: taking glucose to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixes
Closing the volume ratio of water and ethyl alcohol in liquid is 1:4, and obtaining concentration is 0.2mol/L surface modifier；
Again by 10 mL concentration be 0.2 mol/L surface modifier stirring condition under isometric SiO is added into solution2/
Al2O3=46 ZSM-5 molecular sieve, is put into oil bath pan after mixing evenly, and 6 h are stirred at 80 DEG C, is put into 80 in air dry oven
DEG C dry 12 h, then in nitrogen atmosphere at 650 DEG C 4 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface, so
After be applied to catalysis methanol aromatization.
Embodiment 3:
Compound concentration is the rhodamine B solution of 0.5 mol/L, and rhodamine B is taken to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol,
The volume ratio of water and ethyl alcohol is 1:4 in mixed liquor, and obtaining concentration is 0.5mol/L surface modifier；
It is again the rhodamine B solution of 0.5 mol/L by 10 mL concentration, isometric SiO is added into solution under stirring condition2/
Al2O3=27 ZSM-5 molecular sieve, is put into oil bath pan after mixing evenly, and 3 h are stirred at 100 DEG C, are put into air dry oven
90 DEG C of 8 h of drying, then in helium atmosphere encloses at 600 DEG C 6 h of high-temperature process, obtain the modified ZSM-5 molecule in surface
Sieve.Then it is applied to catalysis methanol aromatization.
Embodiment 4:
Compound concentration is the urea liquid of 1.0 mol/L, takes urea to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixed liquor
The volume ratio of middle water and ethyl alcohol is 1:4, and obtaining concentration is 1.0mol/L surface modifier；
It is again the surface modifier of 1.0 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=60
ZSM-5 molecular sieve is put into oil bath pan after mixing evenly, and 4 h are stirred at 100 DEG C, is put into 100 DEG C of dryings in air dry oven
8 h, then in nitrogen atmosphere encloses at 600 DEG C 6 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.Then will
It is applied to catalysis methanol aromatization.
Embodiment 5:
Compound concentration is the thiophene solution of 0.5 mol/L, takes thiophene to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixed liquor
The volume ratio of middle water and ethyl alcohol is 1:4, and obtaining concentration is 0.5mol/L surface modifier；
It is again the surface modifier of 0.5 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=46
ZSM-5 molecular sieve is put into oil bath pan after mixing evenly, and 3 h are stirred at 85 DEG C, is put into 100 DEG C of dryings 8 in air dry oven
H, then in nitrogen atmosphere encloses at 700 DEG C 4 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.Then by it
Applied to catalysis methanol aromatization.
Embodiment 6:
Compound concentration is the glucose solution of 0.4 mol/L, and glucose is taken to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, is mixed
Closing the volume ratio of water and ethyl alcohol in liquid is 1:4, and obtaining concentration is 0.4mol/L surface modifier；
It is again the surface modifier of 0.4 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=104
ZSM-5 molecular sieve, be put into oil bath pan after mixing evenly, 5 h stirred at 70 DEG C, be put into 70 DEG C of dryings in air dry oven
9 h, then in helium atmosphere encloses at 550 DEG C 6 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.Then will
It is applied to catalysis methanol aromatization.
Embodiment 7:
Compound concentration is the melamine solution of 0.8 mol/L, and melamine is taken to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol
In, the volume ratio of water and ethyl alcohol is 1:4 in mixed liquor, and obtaining concentration is 0.8mol/L surface modifier；
It is again the surface modifier of 0.8 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=46
ZSM-5 molecular sieve is put into oil bath pan after mixing evenly, and 5 h are stirred at 60 DEG C, is put into 60 DEG C of dryings 9 in air dry oven
H, then in argon atmosphere is enclosed at 500 DEG C 8 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.Then by it
Applied to catalysis methanol aromatization.
Comparative example 1 ~ 4 is unmodified SiO2/Al2O3=27,46,60,104 ZSM-5 molecular sieve.
The modified ZSM-5 molecular sieve in surface is used as catalyst, and the Evaluation results of catalysis methanol aromatization are shown in Table
1。
Performance evaluation is carried out to the catalyst of embodiment 1 ~ 7 and comparative example 1 ~ 4 respectively, operating process is as follows.It comments every time
The loaded catalyst of valence be 1 g, using pure methanol as raw material, methanol gasifies through 200 DEG C of preheater first, then into
Enter reactor and carry out aromatization, the mass space velocity of methanol is 2.4 h-1, reaction temperature is 420 DEG C, obtained gas-liquid product
After knockout drum separates, gas-phase product is passed directly into GC8600 gas-chromatography and carries out on-line analysis, and liquid product is through grease
By GC7900 gas chromatographic analysis after separation.Finally gas, oil, all products of water are normalized, are indicated with carbon-based mass content,
Catalysis response data result is listed in table 1.
Claims (9)
1. a kind of modified method in ZSM-5 molecular sieve surface, which is characterized in that comprise the steps of: and weigh containing C, N, S element
Surface modifier organic matter, be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, the volume ratio of water and ethyl alcohol is in mixed liquor
1:4, obtains surface modifier, and concentration is 0.1 ~ 1.0 mol/L；Surface modifier is mixed with ZSM-5 molecular sieve again, surface changes
Property agent and ZSM-5 molecular sieve volume ratio be 1:1；After stirring evenly, drying, by obtained solid in atmosphere of inert gases high temperature
Processing makes C, N, S element deposition in molecular sieve surface, obtains the modified ZSM-5 molecular sieve in surface；
The surface modifier organic matter containing C, N, S element is glucose, urea, rhodamine B, thiophene or trimerization as described above
One of cyanamide；
The time stirred after addition ZSM-5 molecular sieve as described above is 3 ~ 8 h, and whipping temp is 60 ~ 100 DEG C；Drying time
For 8 ~ 12 h, drying temperature is 60 ~ 100 DEG C；The high-temperature process time is 4 ~ 8 h, and high-temperature process temperature is 500 ~ 700 DEG C；
Inert gas as described above is nitrogen or helium or argon gas.
2. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1, which is characterized in that
Compound concentration is the glucose solution of 0.1 mol/L: taking glucose to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixes
Closing the volume ratio of water and ethyl alcohol in liquid is 1:4, and obtaining concentration is 0.1mol/L surface modifier；
It is again that isometric SiO is added into solution under 0.1 mol/L surface modifier stirring condition by 10 mL concentration2/Al2O3
=46 ZSM-5 molecular sieve, is put into oil bath pan after mixing evenly, and 8 h are stirred at 60 DEG C, is put into air dry oven 60 DEG C
Dry 12 h, then in nitrogen atmosphere at 550 DEG C 5 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface, then
It is applied to catalysis methanol aromatization.
3. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1, which is characterized in that
Compound concentration is the glucose solution of 0.2 mol/L: taking glucose to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixes
Closing the volume ratio of water and ethyl alcohol in liquid is 1:4, and obtaining concentration is 0.2mol/L surface modifier；
Again by 10 mL concentration be 0.2 mol/L surface modifier stirring condition under isometric SiO is added into solution2/
Al2O3=46 ZSM-5 molecular sieve, is put into oil bath pan after mixing evenly, and 6 h are stirred at 80 DEG C, is put into 80 in air dry oven
DEG C dry 12 h, then in nitrogen atmosphere at 650 DEG C 4 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface, so
After be applied to catalysis methanol aromatization.
4. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1, which is characterized in that
Compound concentration is the rhodamine B solution of 0.5 mol/L, and rhodamine B is taken to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol,
The volume ratio of water and ethyl alcohol is 1:4 in mixed liquor, and obtaining concentration is 0.5mol/L surface modifier；
It is again the rhodamine B solution of 0.5 mol/L by 10 mL concentration, isometric SiO is added into solution under stirring condition2/
Al2O3=27 ZSM-5 molecular sieve, is put into oil bath pan after mixing evenly, and 3 h are stirred at 100 DEG C, are put into air dry oven
90 DEG C of 8 h of drying, then in helium atmosphere encloses at 600 DEG C 6 h of high-temperature process, obtain the modified ZSM-5 molecule in surface
Sieve.
5. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1, which is characterized in that
Compound concentration is the urea liquid of 1.0 mol/L, takes urea to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixed liquor
The volume ratio of middle water and ethyl alcohol is 1:4, and obtaining concentration is 1.0mol/L surface modifier；
It is again the surface modifier of 1.0 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=60
ZSM-5 molecular sieve is put into oil bath pan after mixing evenly, and 4 h are stirred at 100 DEG C, is put into 100 DEG C of dryings in air dry oven
8 h, then in nitrogen atmosphere encloses at 600 DEG C 6 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.
6. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1, which is characterized in that
Compound concentration is the thiophene solution of 0.5 mol/L, takes thiophene to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, mixed liquor
The volume ratio of middle water and ethyl alcohol is 1:4, and obtaining concentration is 0.5mol/L surface modifier；
It is again the surface modifier of 0.5 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=46
ZSM-5 molecular sieve is put into oil bath pan after mixing evenly, and 3 h are stirred at 85 DEG C, is put into 100 DEG C of dryings 8 in air dry oven
H, then in nitrogen atmosphere encloses at 700 DEG C 4 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.
7. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1, which is characterized in that
Compound concentration is the glucose solution of 0.4 mol/L, and glucose is taken to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol, is mixed
Closing the volume ratio of water and ethyl alcohol in liquid is 1:4, and obtaining concentration is 0.4mol/L surface modifier；
It is again the surface modifier of 0.4 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=104
ZSM-5 molecular sieve, be put into oil bath pan after mixing evenly, 5 h stirred at 70 DEG C, be put into 70 DEG C of dryings in air dry oven
9 h, then in helium atmosphere encloses at 550 DEG C 6 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.
8. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1, which is characterized in that
Compound concentration is the melamine solution of 0.8 mol/L, and melamine is taken to be dissolved in the mixed liquor of 1000 milliliters of water and ethyl alcohol
In, the volume ratio of water and ethyl alcohol is 1:4 in mixed liquor, and obtaining concentration is 0.8mol/L surface modifier；
It is again the surface modifier of 0.8 mol/L by 10 mL concentration, isometric SiO is added under stirring condition2/Al2O3=46
ZSM-5 molecular sieve is put into oil bath pan after mixing evenly, and 5 h are stirred at 60 DEG C, is put into 60 DEG C of dryings 9 in air dry oven
H, then in argon atmosphere is enclosed at 500 DEG C 8 h of high-temperature process, obtain the modified ZSM-5 molecular sieve in surface.
9. a kind of modified method in ZSM-5 molecular sieve surface according to claim 1 obtains the modified ZSM-5 molecule in surface
The application of sieve, which is characterized in that be applied to catalysis methanol aromatization.
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| CN111871448A (en) * | 2020-08-03 | 2020-11-03 | 西北大学 | Catalyst for improving oxygen-free aromatization reaction performance of methane and preparation method thereof |
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Application publication date: 20190521 |