CN106215970B - Modified treatment method and application of HZSM-5 molecular sieve catalyst - Google Patents
Modified treatment method and application of HZSM-5 molecular sieve catalyst Download PDFInfo
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
The present invention is based on HZSM-5 molecular sieve common in aromatization of low carbon hydrocarbon technology, it is post-processed using the double modified methods of alkali/vapor, method includes: that HZSM-5 molecular sieve catalyst is added in aqueous slkali to handle, and then carries out steam treatment, modified catalyst is made.Compared with unmodified catalyst, molecular sieve is stripped of framework silicon after alkali process, expands skeleton cellular structure, and formation part is mesoporous, improves and holds charcoal ability；Framework aluminum is removed after steam treatment, modulation acidity ratio enhances anti-carbon deposition ability.Therefore modified catalyst effectively enhances catalytic stability, greatly improves catalyst life, show better aromatization of low carbon hydrocarbon reactivity worth while improving aromatization activity.
Description
Technical field
The present invention relates to light-hydrocarbon aromatized catalytic field, specially a kind of modification side of HZSM-5 molecular sieve catalyst
Method and its application in aromatization of low carbon hydrocarbon.
Background technique
Aromatic hydrocarbons is the most basic raw material of Organic Chemical Industry, is mainly derived from petroleum and coal tar.Benzene, first in aromatic hydrocarbons
Benzene, dimethylbenzene are the important base stocks of petrochemical industry, and yield and scale are inferior to ethylene and propylene.The maximum purposes of benzene is
Produce styrene, it is aggregated that polystyrene, followed by producing cyclohexane by benzene hydrogenation can be obtained, by cyclohexane oxidation-cyclohexanone-oneself
The preparation route of interior phthalein amine is for producing nylon.It is paraxylene that dosage is maximum in dimethylbenzene, be can be made into pair through high-temperature oxydation
Phthalic acid is the primary raw material that synthesis gathers cruel terylene, and terylene accounts for 63% in the yield of world's synthetic fibers.
The light hydrocarbon feedstocks such as liquefied petroleum gas (LPG), light olefin, Aromatic raffinate should not make reformer feed, but can pass through virtue
Structure chemical industry skill is converted into aromatic hydrocarbons, improves its added value.Industrial light-hydrocarbon aromatized technology mainly includes BP and Uop Inc.'s connection at present
Run adding using LPG as what the Cyclar technique of raw material, Exxon Mobil and Asahi Chemical company developed respectively for hair jointly
Work is rich in the M2-Forming technique and Alpha ARO technique of olefin feed.
HZSM-5 molecular sieve has unique pore structure and preferable thermal stability, is the tradition of aromatization of low carbon hydrocarbon reaction
Catalyst.But due to its stronger solid acid, the low-carbon hydrocarbon pyrolysis is easily caused in catalysis reaction and forms carbon deposit and inactivates, or
Person's lower carbon number hydrocarbons is reacted via carbonium ion or dehydrogenation reaction generates alkene and then the oligomerisation generation macromolecule polyalcohol on acid site
And lead to coking and deactivation.In order to improve the catalytic stability of HZSM-5 molecular sieve, frequently with simple process, cheap rear place
Logos (steam treatment, alkali process etc.).Suitable steam treatment can reduce the acid strength and acid amount of catalyst, improve its
Catalytic stability in aromatization, and moderate alkali process method can be before not destroying the original characteristic crystal structure of molecular sieve
It puts, forms molecular sieve desiliconization a certain amount of effectively mesoporous, while improving Molecular Sieve Acid Density, reduce catalysis reaction and expand
Resistance is dissipated, to improve the activity and stability of catalyst.
A kind of catalyst and preparation method thereof of carbon 4 liquid gas aromatization is disclosed in CN200410050202.3, is catalyzed
After the ZSM-5 molecular sieve and aluminium oxide that agent is 10 ~ 500nm of grain size are with the weight ratio mixed-forming of 1:9 ~ 9:1, it is with concentration
The ammonium ion solution of 0.1 ~ 1.0M is exchanged into hydrogen type catalyst, and steam treatment 5min ~ 200h is then used at 400-800 DEG C,
Then at 1 ~ 80 DEG C with acid solution carry out 0.5 ~ 200h acid handle, gained catalyst can 300 ~ 500 DEG C, 0.1 ~ 5Mpa,
Feed space velocities are 0.05 ~ 20h-1And under conditions of no carrier gas, liquefied gas through aromatization is made in fixed bed reactors.
A kind of modified ZSM-5 type molecular sieve catalyst that can be used for preparing propylene from methanol is disclosed in CN200810188464.4
And preparation method thereof, catalyst is the type ZSM 5 molecular sieve that calcination process is crossed, and Si/Al atomic ratio is greater than 100, grain size
In 0.2 ~ 2 micron of range, modification mode is sour modification, first alkali modification again after sour modification and modification
One or more alkaline-earth metal or rare earth metal are added in a manner of ion exchange or incipient impregnation.
A kind of molecular sieve catalyst for carbon 4 liquid gas aromatization reaction is disclosed in CN200810010622.7
Preparation method, catalyst are rare earth-ZSM-5/ZSM-11 cocrystallization molecular sieve, after catalyst and aluminium oxide and water mixed-forming,
1 ~ 10h is handled at 45 ~ 100 DEG C with the aqueous slkali of 0.05 ~ 2.0M, is then exchanged into the ammonium nitrate solution of 0.5 ~ 1.0mol/L
Hydrogen type catalyst is then passed through 400 ~ 700 DEG C of high-temperature vapors and handles 1 ~ 10h, 0.5 ~ 25.0wt% of final impregnating metallic zinc and
Under the conditions of 400 ~ 700 DEG C roast 1 ~ 10h, gained catalyst can 470 ~ 540 DEG C, 0.2 ~ 0.9MPa, Feed space velocities be 0.2 ~
1.5h-1Under conditions of, liquefied gas through aromatization is made in fixed bed reactors.
A kind of alkali-acid method of modifying of ZSM-5 zeolite molecular sieve is disclosed in CN201310552135.4, first using organic
The mixed solution (molar ratio is 0 ~ 1) of alkali and inorganic base carries out alkali modification, OH to ZSM-5 zeolite molecular sieve-Concentration 0.05 ~
ZSM-5 and mixed ammonium/alkali solutions are stirred 10 ~ 480min at 25 ~ 95 DEG C by 0.5M range, and the sour modification after alkali modification is 0.05
5 ~ 360min of stir process, gained catalyst are farthest protected while manufacturing mesoporous in ~ 1M organic acid, at 25 ~ 95 DEG C
Stay microcellular structure.
A kind of modified zsm-5 zeolite and method of modifying are disclosed in CN201410080934.0, according to 10 ~ 120mL/g
Liquid-solid ratio ZSM-5 molecular sieve is added in acid solution, 1 ~ 8h is stirred under the conditions of 20 ~ 100 DEG C, is pressed after weak acid scrubbing 2 ~ 5 times
The modified modified ZSM-5 of acid is added in aqueous slkali according to the liquid-solid ratio of 10 ~ 120mL/g, stirs 0.5 under the conditions of 20 ~ 100 DEG C
~ 4h, through drying, roasting, ion exchange after weak acid scrubbing 2 ~ 5 times, the most probable pore size of gained modified ZSM-5 is 4 ~ 12nm, Jie
Pore specific surface area is 300 ~ 400m2/ g, partial size are 0.1 ~ 10 μm, and the anti-of preparing gasoline by methanol can be carried out in fixed bed reactors
It answers.
A kind of -5 zeolite catalyst of modified no-adhesive ZSM-5 and preparation method thereof is disclosed in CN200610147672.0,
High-temperature water heat treatment first is carried out to spherical adhesiveless ZSM-5, then carries out sour processing, obtained modified ZSM-5 catalyst grain
Diameter is 0.5 ~ 2nm, silica alumina ratio is that 20 ~ 300, specific surface area is higher than 350m2/ g can carry out ethyl alcohol on fixed bed reactors
It is dehydrated ethylene reaction produced.
Summary of the invention
The object of the present invention is to provide the molecular sieve catalysts of a kind of raising aromatization of low carbon hydrocarbon catalytic activity and stability
Preparation method, its aromatization of low carbon hydrocarbon catalytic is improved particular by alkali process-steam treatment HZSM-5 molecular sieve
The method of energy.
The present invention is achieved by the following technical scheme:
A kind of modification processing method of HZSM-5 molecular sieve catalyst, includes the following steps:
(1), HZSM-5 molecular sieve catalyst is placed in the aqueous slkali of 0.01 ~ 1.0M, at 50 ~ 100 DEG C stir 0.5 ~
8h；
(2), the product of step (1) is neutralized to neutrality with acid, with the ammonium nitrate solution of 0.1 ~ 1.0M in 70 ~ 90 DEG C of ions
HZSM-5 molecular sieve catalyst is made in 400 ~ 700 DEG C of 2 ~ 6h of roasting after drying in exchange；
The product that (3) obtain step (2) is 1 ~ 50h by air speed-1, temperature be 200 ~ 600 DEG C of steam treatment,
The processing time is 0.5 ~ 20h, catalyst needed for being made.
Aqueous slkali in step (1) is NaOH, Na2CO3、KOH、NaHCO3One or more of solution.
It is applied in aromatization of low carbon hydrocarbon reaction using the HZSM-5 molecular sieve catalyst of above method preparation.
Above-mentioned catalyst modification method is by HZSM-5 molecular sieve catalyst by certain temperature, concentration, the alkali under the time
Solution processing is neutralized to neutrality with acid later, and ammonium ion exchange, dry, roasting obtain hydrogen type molecular sieve, then in certain temperature
Steam treatment finished product catalyst is carried out under degree, time, air speed.
Advantage of this approach is that molecular sieve is stripped of part framework silicon after alkali process compared with unmodified catalyst, expand
Big skeleton cellular structure, it is mesoporous to form part, improves and holds charcoal ability；Framework aluminum is removed after steam treatment, modulation is acid
Ratio enhances anti-carbon deposition ability.Therefore modified catalyst while improving aromatization activity, stablize by effectively enhancing catalysis
Property, catalyst life is greatly improved, better aromatization of low carbon hydrocarbon catalytic performance is shown.
Detailed description of the invention
Fig. 1 shows the XRD diffracting spectrums of embodiment 1 and 1 ~ 2 gained catalyst of comparative example.
The graph of pore diameter distribution of Fig. 2 expression embodiment 1 and 1 ~ 2 gained catalyst of comparative example.
The NH of Fig. 3 expression embodiment 1 and 1 ~ 2 gained catalyst of comparative example3- TPD result.
The pyridine infrared spectrogram of Fig. 4 expression embodiment 1 and 1 ~ 2 gained catalyst of comparative example.
Fig. 5 a indicates iso-butane conversion ratio changing rule of the resulting catalyst of embodiment 1 ~ 5 in aromatization.
Fig. 5 b indicates that the iso-butane conversion ratio of embodiment 1 and the resulting catalyst of comparative example 1 ~ 2 in aromatization becomes
Law.
Fig. 6 a indicates liquid yield changing rule of the resulting catalyst of embodiment 1 ~ 5 in aromatization.
Fig. 6 b indicates that the liquid yield of embodiment 1 and the resulting catalyst of comparative example 1 ~ 2 in aromatization changes and advises
Rule.
Fig. 7 a indicates BTX selectivity changing rule of the resulting catalyst of embodiment 1 ~ 5 in aromatization.
Fig. 7 b indicates that the BTX of embodiment 1 and the resulting catalyst of comparative example 1 ~ 2 in aromatization selectively variation is advised
Rule.
Fig. 8 shows 1 gained catalyst one way in aromatization of embodiment react iso-butane conversion ratio to inactivation with
Liquid yield changing rule.
Specific embodiment
Specific embodiments of the present invention are further elaborated with reference to the accompanying drawing.
Embodiment 1
A kind of modification processing method of HZSM-5 molecular sieve catalyst, includes the following steps:
(1), by a certain amount of commercialization HZSM-5 molecular sieve catalyst of purchase in the NaOH solution of 0.2M, 80 DEG C of thermostatted waters
Bath stirring 2h；
(2), it is neutralized to neutrality with acid, is used 1M ammonium nitrate solution ion exchange 3 times at 70 DEG C, 120 DEG C of dryings, 520 DEG C
3h is roasted, H-type molecular sieve is obtained；
(3), in 450 DEG C of steam treatment 4h, air speed 3h-1, resulting catalyst is denoted as catalyst A.
Embodiment 2
Steam treatment temperature in embodiment 1 is changed to 300 DEG C, remaining condition is all the same, obtains sample used, note
Make catalyst B.
Embodiment 3
Steam treatment temperature in embodiment 1 is changed to 600 DEG C, remaining condition is all the same, obtains sample used, note
Make catalyst C.
Embodiment 4
The steam treatment time in embodiment 1 is changed to 2h, remaining condition is all the same, obtains sample used, is denoted as
Catalyst D.
Embodiment 5
The steam treatment time in embodiment 1 is changed to 8h, remaining condition is all the same, obtains sample used, is denoted as
Catalyst E.
In order to be compareed with above-mentioned alkali-vapor modified HZSM-5, unmodified HZSM-5 and modified sequence are inverted
Vapor-alkali modification HZSM-5 molecular sieve as a comparison case.
Comparative example 1
Unmodified HZSM-5 catalyst is denoted as catalyst F.
Comparative example 2
By a certain amount of HZSM-5 molecular sieve catalyst 450 DEG C steam treatment 4 hours, air speed 3h-1, products obtained therefrom
In the NaOH solution of 0.2M, 2h is stirred in 80 DEG C of waters bath with thermostatic control, is neutralized to neutrality with acid, and the ammonium nitrate solution of 1M is used at 70 DEG C
Ion exchange 3 times, 120 DEG C of dryings, 520 DEG C of roasting 3h, obtained vapor-alkali modification HZSM-5 catalyst is denoted as catalyst G.
The evaluation of catalyst aromatization activity
Embodiment 1 ~ 5 and the resulting catalyst of comparative example 1 ~ 2 are respectively placed in the stainless steel reaction pipe that internal diameter is 8mm,
Catalyst performance evaluation is carried out in fixed bed reactors, the loadings of catalyst are 2g, in N2It is reacted, is reacted under atmosphere
Condition is 530 DEG C, 0.3MPa, WHSV=3h-1.Reaction raw materials are 99.5% iso-butane.Product after reaction is separated through cold-trap to be used
Gas chromatographic analysis, gas phase hydrocarbon GDX-103 packed column；Liquid phase hydro carbons composition FFAP capillary column (30m × 0.32mm ×
0.25 μm) separation.
Aromatization of low carbon hydrocarbon catalytic performance on A ~ G catalyst is compared, as a result as illustrated in figs. 5-7, with catalyst B
For ~ G compared to the high conversion rate on catalyst A, liquid yield is high, and BTX selectivity is high.Catalyst A is enterprising in fixed bed reactors
Row performance evaluation is until inactivation, and as a result such as Fig. 8, the aromatization stability of catalyst are significantly improved, one way reaction
Service life reaches 312h, is much higher than commercial catalysts F.
Catalyst performance characterization
Structure and acid characterization are carried out to embodiment 1 and the resulting catalyst of comparative example 1 ~ 2, as a result such as Fig. 1 ~ 4 and table 1.
Catalyst A relative crystallinity is higher, has certain mesoporous amount, and strong, weak acid amount and B/L acid ratio are suitable.
1 embodiment and comparative example of table is related to the acid amount distribution of catalyst
Embodiment 6
A kind of modification processing method of HZSM-5 molecular sieve catalyst, includes the following steps:
(1), HZSM-5 molecular sieve catalyst is placed in the Na of 0.1M2CO3In solution, 6h is stirred at 100 DEG C；
(2), the product of step (1) is neutralized to neutrality with acid, with the ammonium nitrate solution of 0.5M in 75 DEG C of ion exchanges 3
It is secondary, in 400 DEG C of roasting 2h after drying, HZSM-5 molecular sieve catalyst is made；
The product that (3) obtain step (2) is 40h by air speed-1, temperature be 500 DEG C of steam treatment, when processing
Between be 15h, be made needed for catalyst.
Embodiment 7
A kind of modification processing method of HZSM-5 molecular sieve catalyst, includes the following steps:
(1), HZSM-5 molecular sieve catalyst is placed in the KOH solution of 0.01M, stirs 0.5h at 90 DEG C；
(2), the product of step (1) is neutralized to neutrality with acid, with the ammonium nitrate solution of 0.3M in 90 DEG C of ion exchanges 3
It is secondary, in 700 DEG C of roasting 5h after drying, HZSM-5 molecular sieve catalyst is made；
The product that (3) obtain step (2) is 1h by air speed-1, temperature be 300 DEG C of steam treatment, handle the time
For 30h, catalyst needed for being made.
Embodiment 8
A kind of modification processing method of HZSM-5 molecular sieve catalyst, includes the following steps:
(1), HZSM-5 molecular sieve catalyst is placed in the NaHCO of 0.5M3In solution, 1h is stirred at 60 DEG C；
(2), the product of step (1) is neutralized to neutrality with acid, with the ammonium nitrate solution of 0.1M in 85 DEG C of ion exchanges 3
It is secondary, in 600 DEG C of roasting 6h after drying, HZSM-5 molecular sieve catalyst is made；
The product that (3) obtain step (2) is 10h by air speed-1, temperature be 400 DEG C of steam treatment, when processing
Between be 0.5h, be made needed for catalyst.
Embodiment 9
A kind of modification processing method of HZSM-5 molecular sieve catalyst, includes the following steps:
(1), HZSM-5 molecular sieve catalyst is placed in the KOH solution of 1M, stirs 5h at 50 DEG C；
(2), the product of step (1) is neutralized to neutrality with acid, with the ammonium nitrate solution of 0.2M in 80 DEG C of ion exchanges 3
It is secondary, in 500 DEG C of roasting 2.5h after drying, HZSM-5 molecular sieve catalyst is made；
The product that (3) obtain step (2) is 50h by air speed-1, temperature be 200 DEG C of steam treatment, when processing
Between be 1h, be made needed for catalyst.
In short, this method is based on HZSM-5 molecular sieve common in aromatization of low carbon hydrocarbon technology, using alkali/vapor
Double modified methods post-process it, i.e., HZSM-5 molecular sieve catalyst are added in aqueous slkali and handle, then carry out water
Modified catalyst is made in steam treated.Compared with unmodified catalyst, molecular sieve is stripped of framework silicon after alkali process, expands
Skeleton cellular structure, formation part is mesoporous, improves and holds charcoal ability；Remove framework aluminum after steam treatment, modulation acidity ratio,
Enhance anti-carbon deposition ability.Therefore modified catalyst effectively enhances catalytic stability, pole while improving aromatization activity
The earth improves catalyst life, shows better aromatization of low carbon hydrocarbon reactivity worth.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although ginseng
According to embodiment, the present invention is described in detail, those skilled in the art should understand that, to technical solution of the present invention
It is modified or replaced equivalently, without departure from the spirit and scope of technical solution of the present invention, should all cover of the invention
In claims.
Claims (1)
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| CN107051577B (en) * | 2017-03-22 | 2020-12-18 | 大连理工大学 | A kind of preparation method of low-carbon hydrocarbon aromatization catalyst and application thereof |
| CN108246346A (en) * | 2018-01-26 | 2018-07-06 | 中国科学院大连化学物理研究所 | For methacrylaldehyde, the method for modifying of propionic aldehyde and ammonia reaction ZSM-11 molecular sieve catalysts |
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| CN108889333B (en) * | 2018-07-05 | 2021-06-01 | 中国矿业大学 | Method for preparing solid acid catalyst by loading sulfated zirconia on HZSM-5 molecular sieve and application |
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| CN113694959A (en) * | 2020-05-22 | 2021-11-26 | 南京工业大学 | Catalyst for preparing nonene by propylene oligomerization reaction and preparation method thereof |
| CN115591570B (en) * | 2021-06-28 | 2024-03-29 | 中国石油化工股份有限公司 | Ten-membered ring molecular sieve catalyst, preparation method and application thereof, and aromatic hydrocarbon alkylation method |
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| "An effective method to enhance the stability on-stream;Yueqin Song et.al;《Applied Catalysis A: General》;20060126;第302卷(第1期);第70页左栏第3段、77页左栏第4段-右栏第1段 * |
| "ZSM-5分子筛的碱处理条件对丁烯芳构化反应性能的影响";宋月芹等;《分子催化》;20070831;第21卷;第105页左栏第2段，第106页左栏最后一段 * |
| ZSM-5分子筛的脱硅改性好加氢改质性能;石冈等;《燃料化学学报》;20130531;第41卷(第5期);全文 * |
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