CN103894222A - Modified zeolite catalyst for preparing propylene through methanol dehydration and preparation method of modified zeolite catalyst - Google Patents
Modified zeolite catalyst for preparing propylene through methanol dehydration and preparation method of modified zeolite catalyst Download PDFInfo
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- CN103894222A CN103894222A CN201210588048.XA CN201210588048A CN103894222A CN 103894222 A CN103894222 A CN 103894222A CN 201210588048 A CN201210588048 A CN 201210588048A CN 103894222 A CN103894222 A CN 103894222A
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- zeolite catalyst
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Abstract
The invention discloses a modified ZSM-5 zeolite catalyst for a catalytic reaction for preparing propylene through methanol as well as a preparation method of the catalyst. The catalyst is formed by introducing controllable acid site through aluminum atom hybrid modification by taking all-silicon ZSM-5 zeolite as the basis. The catalyst is moderate in acidity and is particularly favorable for methanol conversion, and the propylene is produced at high selectivity. The catalyst is high in catalytic activity, the reaction conversion rate is high, and the stable period is long. The 30-100 mass percent of methanol serves as a reaction raw material, the one-way service life is longer than 80 hours, the selectivity of the propylene is more than 48 percent, the regeneration method is simple, and the regeneration performance is well restored.
Description
Technical field
The present invention relates to industrial circle, relate to specifically a kind of Catalysts and its preparation method of methanol dewatered propylene.
Background technology
Zeolite molecular sieve is a kind of inorganic silicon aluminate crystal, in skeleton, contain the duct (ca.0.3-1.5nm) of the molecular dimension of regular and ordered arrangement, there is the effect of grading of shape selective catalysis, ion-exchange and molecular sieve, be widely used in the industrial process such as catalysis, adsorbing separation and ion-exchange.
Mobil company is in ZSM-5 zeolite (MFI type) molecular sieve [U.S. Patent No. 3702886 of report in 1972,1972], there is (ten-ring straight hole road, two-dimentional ten-ring duct, aperture is the sinusoidal duct of 0.54nm × 0.56nm and ten-ring, aperture is 0.51nm × 0.54nm), be the catalysis material being most widely used up to now, in petroleum streams fluidized catalytic cracking (FCC), hydrocracking and in the oil refining process such as refining, used in a large number.Catalytic field in petrochemical industry, fine chemistry industry and environmental protection etc. also has numerous important application.Hydrogen ZSM-5(H-ZSM-5) zeolite catalyst heat endurance and hydrothermal stability high, framework si-al ratio can regulate and control in a big way, surface has stronger acidity, conventionally product is had to higher activity and selectivity.For improving its catalysis in some specific reaction, often need to carry out modification to adjust surface acidity (acid amount and acid strength).Method of modifying mainly contains the chemical erosion such as steam treatment and acid treatment processing, or the two is combined to remove framework aluminum, reduces acid amount and improves acid strength [Chinese patent 200610147672.0].Framework dealumination meeting partial destruction zeolite molecular sieve lattice, forms skeleton defect, and the catalyst of making is easily coking in catalytic reaction, thereby reduces its active stability.And regeneration frequently can destroy its skeleton structure, reduce heat endurance and the hydrothermal stability of catalyst, shorten its service life.
Containing oxygen alcohol compound Dehydration alkene, as industrial crude preparing olefin by methyl alcohol dewatering (MTO), the methanol dewatered propylene of industrial crude (MTP), the catalytic reaction of Diluted Alcohol Dehydration ethene (ETE), be in current non-petroleum technology with the core technology of ICL for Indirect Coal Liquefaction alkene processed and bio-ethanol alkene petroleum replacing processed route, strategic importance and using value are important.ZSM-5 zeolite molecular sieve all shows good catalytic performance in above-mentioned catalytic reaction, compared with traditional acidic alumina dehydration catalyst, and reactivity and selectively higher.In MTP reaction, show the advantage [the open CN101269340A of patent] of high Propylene Selectivity and high propylene/ethylene ratio at the ZSM-5 zeolite catalyst that uses binder free technology to prepare, but continuous catalytic reaction products yield easily fluctuates, less stable.
Therefore, there is at present the demand for the Catalysts and its preparation method for methanol dewatered propylene of improvement in performance.
Summary of the invention
An object of the present invention is to provide a kind of new modified ZSM-5 zeolite catalyst, it can be applicable to MTP catalytic reaction.Another object of the present invention also provides the preparation method of this catalyst.Another object of the present invention has been to provide the renovation process of described catalyst.In addition, the present invention also aims to provide the application of this catalyst.
For above object, the technical scheme that the present invention takes is as follows:
On the one hand, the invention provides a kind of zeolite catalyst for methanol dewatered propylene, described catalyst, using total silicon zeolite as substrate, through aluminium atom hydridization, forms acid suitable modified zeolite catalyst.
Preferred zeolite is ZSM-5 zeolite;
ZSM-5 zeolite used is complete silicon structure, does not contain aluminium element;
ZSM-5 zeolite, through metallic aluminium salt solution impregnation, then in closed reactor heating, takes out post-drying, obtains ZSM-5 zeolite catalyst, its skeleton SiO after high-temperature roasting
2/ Al
2o
3scope is at 100-1000.
On the other hand, the invention provides the method for preparing above-mentioned catalyst take aluminium colloidal sol as binding agent, it can be applicable to MTP catalytic reaction.Said method comprising the steps of:
One or more in use aluminum sulfate, aluminium chloride or aluminum nitrate are configured to aluminium salt working solution;
Wherein, aluminium salt work solution concentration represents with Al ion molar concentration, the preferred 0.05-1mol/L of concentration.
Zeolite is mixed with aluminium salt working solution, and wherein the weight ratio of zeolitic material and aluminium salt working solution is 1:2-1:10.
After zeolite is mixed with aluminium salt working solution, be positioned in autoclave, add thermal response after airtight in baking oven, wherein reaction temperature is 100-200 ℃, and the heat time is 12-48 hour.
Reaction completes, and mixture is taken out from reactor, in 90-120 ℃ of oven for drying.
Solid sample after drying is placed in to 300-550 ℃ of Muffle furnace roasting 1-10 hour.
ZSM-5 zeolite catalyst, after aluminium is atom modified, wherein contains the framework aluminum of four-coordination framework aluminum, pentacoordinate and the non-framework aluminum of hexa-coordinate.
In addition, described catalyst can also be regenerated by the method comprising the following steps:
Control beds 300-350 ℃, with 5%-10%O
2(N
2for carrier gas) 10-50mL/min purges 1-5 hour; Be warmed up to 400-450 ℃, with 5%-20%O
2(N
2for carrier gas) 10-50mL/min purges 1-5 hour; Be warmed up to 500-550 ℃, with 5%-40%O
2(N
2for carrier gas) 10-50mL/min purges 1-5 hour, 10%-50%O
2(N
2for carrier gas) 50-100mL/min purges 1-10 hour.
Another aspect, the present invention also provides the purposes of described catalyst in the reaction of preparing propylene; Preferably, described reaction is methanol dewatered propylene.
According to the specific embodiment of the present invention, the feature of modified ZSM-5 zeolite catalyst provided by the present invention can characterize with the following method:
1, powder x-ray diffraction (XRD).In powder x-ray diffraction, reference standard collection of illustrative plates, to determine the structure of ZSM-5 zeolite and the existence form of aluminium oxide in this catalyst.
2, XRF scattering analysis (XRF).Measure the chemical composition of catalyst, to calculate the apparent chemical ratio of Al to Si of catalyst.
3,
27al nuclear magnetic resonance (
27al NMR).The co-ordination state of the aluminium of analysis of catalyst.
4, nitrogen absorption under low temperature.Characterize specific area and the pore volume of catalyst.
5、NH
3-TPD。Measure modified catalyst surface acid intensity and solid acid amount.
6, MTP catalytic property characterizes.Characterize the activity and selectivity of catalyst in MTP reaction.
Existing method of modifying mainly contains the chemical erosion such as steam treatment and acid treatment processing, or the two is combined to remove framework aluminum, reduces acid amount and improves acid strength.Framework dealumination meeting partial destruction zeolite molecular sieve lattice, forms skeleton defect, and the catalyst of making is easily coking in catalytic reaction, thereby reduces its active stability.And regeneration frequently can destroy its skeleton structure, reduce heat endurance and the hydrothermal stability of catalyst, shorten its service life.
Therefore compared to the prior art, modified ZSM-5 zeolite catalyst provided by the invention and its preparation method have following three advantages:
The first, the substrate of catalyst of the present invention is total silicon ZSM-5 zeolite crystal, adopts the mode of aluminium atom hydridization to introduce framework aluminum and non-framework aluminum.Experiment showed, through aluminium atom modifiedly, acidity of catalyst is moderate, and duct is open, and specific area is high, and molecular diffusivity is good, is particularly conducive to preparing propylene from methanol catalytic reaction.
The second, catalyst of the present invention is applied to MTP reaction, and catalytic activity, methyl alcohol average conversion and Propylene Selectivity are high, and the stable period of catalytic reaction high conversion is long, and slowly, the time of maintenance 98% above conversion ratio is long in methanol conversion decay.
Three, compared with existing catalyst, catalyst recovery process of the present invention is simple, and after regeneration, performance recovery is good.
In a word, catalyst activity of the present invention is good, and reaction conversion ratio is high, and stable period is long.Take mass concentration 30-100% methyl alcohol as reaction raw materials, single pass life is greater than 800 hours, and Propylene Selectivity is greater than 48%, and renovation process is simple, and it is good that regenerability is recovered.
Accompanying drawing explanation
Below, describe by reference to the accompanying drawings embodiments of the invention in detail, wherein:
Fig. 1 is the XRD spectra of catalyst of the present invention;
Fig. 2 is the NH of catalyst of the present invention
3-TPD spectrogram.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention, but these embodiment only limit to explain the present invention, and be not used in restriction the present invention.The experimental technique of not marked specific experiment condition in embodiment below, conventionally according to normal condition, or the condition of advising according to manufacturer, in following examples, the variation of technical scheme is all in protection scope of the present invention.
embodiment 1-9: the preparation of aluminium salt working solution
Prepare typical feedstock that aluminium salt working solution adopts and proportioning, preparation condition etc. and see the following form 1.
The preparation of table 1, aluminium salt working solution
Preparation process is as follows:
Take embodiment 1 as example, take 17.1 grams, anhydrous slufuric acid aluminium, import beaker, add suitable quantity of water to dissolve, after dissolving completely, pour 1L volumetric flask into, be settled to 1L.
embodiment 10-18: catalyst hydrothermal modification
See the following form 2 with the representative condition of aluminum salt solution hydrothermal modification:
Table 2, catalyst hydrothermal modification
| Embodiment | Working solution | Solid-liquid mass ratio |
| 10 | Embodiment 1 | 1:10 |
| 11 | Embodiment 2 | 1:5 |
| 12 | Embodiment 2 | 1:3 |
| 13 | Embodiment 3 | 1:2 |
| 14 | Embodiment 5 | 1:5 |
| 15 | Embodiment 7 | 1:8 |
| 16 | Embodiment 7 | 1:10 |
| 17 | Embodiment 9 | 1:2 |
| 18 | Embodiment 9 | 1:5 |
Preparation process is as follows:
Take embodiment 12 as example, take 100 grams, dry ZSM-5 zeolite powder (Shanghai Fu Xu molecular sieve Co., Ltd), move into beaker, take 300 grams of working solutions that embodiment 2 configures and pour above-mentioned beaker into, stir evenly rear stand-by.
embodiment 19: catalyst has been prepared and performance evaluation
The mixture that embodiment 12 is obtained moves into the autoclave of 500mL, after sealing with 180 ℃ of baking ovens, heat 24 hours, after finishing, reaction pours mixture in still into crucible, be positioned over 100 ℃ of oven for drying moisture, proceed to again 550 ℃ of Muffle furnace roastings 5 hours, obtain the catalyst of having prepared.
The physico-chemical property and the catalytic performance that make catalyst are analyzed, and result is as follows:
Fig. 1 is the XRD spectra of catalyst.Can find out that this catalyst is typical MFI structure type molecular sieve, degree of crystallinity is higher, through XRF elementary analysis, and its SiO
2/ Al
2o
3be 120.5 than (SAR).Have no the characteristic diffraction peak of obvious aluminium oxide, illustrate that aluminium salt is stored in zeolitic material with the state of high dispersive after high-temperature roasting, does not form other crystal structure.
27al NMR analysis result shows that the co-ordination state of Al, take four-coordination as main, containing a small amount of hexa-coordinate and pentacoordinate form, illustrates that most of aluminium enters zeolitic frameworks, exists on a small quantity with the non-skeleton form of alundum (Al2O3).
This catalyst of nitrogen absorption under low temperature digital proof of catalyst presents typical I type adsorption curve, and BET specific area and total hole volume are respectively 360m
2/ g and 0.25cm
3/ g, illustrates that its perfect structure and duct are open.
Fig. 2 is the NH of catalyst
3-TPD spectrogram.To obviously move to high temperature direction corresponding to the desorption peaks of weak acid position compared with near 200 ℃, total silicon ZSM--5 zeolite near the desorption peaks 280 ℃, illustrate with the faintly acid of aluminium colloidal sol moulded zeolite catalyst and be enhanced; Meanwhile, occur a large Bao Feng, and have no obvious high temperature strong acidic site desorption peaks 400-800 ℃ of scope, the acid site that occurs a large amount of moderate strengths in catalyst is described, the corresponding desorption peaks desorption peaks corresponding with strong acid center forms overlapping and cannot separate.But it is less in the Acidity of entirety, still to show as weak acid center, and strong acid center is many, occurs the characteristic in a certain amount of moderate strength acid site.
embodiment 20: the catalytic effect examination of catalyst
Catalyst 120g prepared by embodiment 18 loads in fixed bed reactors, take the industrial methanol of mass concentration 90% as raw material, and mass space velocity 1h when methanol solution
-1, under 480 ℃ of reaction temperatures, carry out catalysis examination.Methyl alcohol average conversion is more than 98% in 800 hours for this catalyst, and its activity keeping is stable; Ethene average selectivity is about 6.8%, and propylene average selectivity is 48.6%.
embodiment 21: the regeneration of catalyst
After the catalytic reaction of embodiment 20 stops, controlling 350 ℃ of beds, with 5%O
2(95%N
2) 20mL/min purge 2 hours; Be warmed up to 450 ℃, with 5%O
2(95%N
2) 20mL/min purge 2 hours; Be warmed up to 550 ℃, with 10%O
2(90%N
2) 20mL/min purge 2 hours, 10%O
2(90%N
2) 50mL/min purges 5 hours, to the catalyst processing of regenerating.
embodiment 22: the catalytic effect examination of catalyst regeneration
After embodiment 21 regeneration endings, control 480 ℃ of temperature of reactor, take the industrial methanol of mass concentration 90% as raw material, mass space velocity 1h when methanol solution
-1again carry out catalytic evaluation, catalyst activity recovers substantially completely, still keeps methyl alcohol average conversion more than 99% in 600 hours, ethene average selectivity 7.2%, propylene average selectivity 48.5%.Catalytic reaction result and fresh catalyst reaction result are basically identical, illustrate that processing catalyst activity through regeneration recovers completely.
Claims (3)
1. for a zeolite catalyst for methanol dewatered propylene, it is characterized in that this zeolite catalyst is using total silicon zeolite as substrate, forms through aluminium atom hydridization.
2. the zeolite catalyst for methanol dewatered propylene according to claim 1, is characterized in that described zeolite is ZSM-5 zeolite.
3. a method of preparing zeolite catalyst described in claim 1 or 2, is characterized in that the method is:
Zeolite is mixed with aluminium salt working solution, be positioned in autoclave, add thermal response after airtight in baking oven, wherein reaction temperature is 100-200 ℃, and the heat time is 12-48 hour;
Reaction completes, and mixture is taken out from reactor, in 90-120 ℃ of oven for drying;
Solid after drying is placed in to 300-550 ℃ of Muffle furnace roasting 1-10 hour;
Wherein said aluminium salt working solution is: one or more in aluminum sulfate, aluminium chloride or aluminum nitrate are configured to.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210588048.XA CN103894222B (en) | 2012-12-29 | 2012-12-29 | For the modified zeolite catalyst and preparation method thereof of methanol dewatered propylene |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140268A (en) * | 2015-04-02 | 2016-11-23 | 中国石油大学(华东) | Preparing propylene by methanol transformation silica zeolite catalyst and preparation method thereof |
| CN108940356A (en) * | 2018-05-29 | 2018-12-07 | 广东工业大学 | A kind of preparation method of Fe@ZSM-11 mesoporous molecular sieve catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045930A (en) * | 1990-03-15 | 1990-10-10 | 南开大学 | The catalyzer that is used for the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation |
| CN101269340A (en) * | 2008-04-30 | 2008-09-24 | 复旦大学 | High silicon-aluminum ratio ZSM-5 zeolite catalyst, preparation method and application thereof |
| KR20080113565A (en) * | 2007-06-25 | 2008-12-31 | 에스케이에너지 주식회사 | Preparation method of the zeolite containing iron catalyst for scr(selective catalyst reaction) |
| CN102059138A (en) * | 2010-11-18 | 2011-05-18 | 大唐国际化工技术研究院有限公司 | ZSM-5 zeolite catalyst for preparing propylene by methanol dehydration as well as preparation method and application thereof |
-
2012
- 2012-12-29 CN CN201210588048.XA patent/CN103894222B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045930A (en) * | 1990-03-15 | 1990-10-10 | 南开大学 | The catalyzer that is used for the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation |
| KR20080113565A (en) * | 2007-06-25 | 2008-12-31 | 에스케이에너지 주식회사 | Preparation method of the zeolite containing iron catalyst for scr(selective catalyst reaction) |
| CN101269340A (en) * | 2008-04-30 | 2008-09-24 | 复旦大学 | High silicon-aluminum ratio ZSM-5 zeolite catalyst, preparation method and application thereof |
| CN102059138A (en) * | 2010-11-18 | 2011-05-18 | 大唐国际化工技术研究院有限公司 | ZSM-5 zeolite catalyst for preparing propylene by methanol dehydration as well as preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140268A (en) * | 2015-04-02 | 2016-11-23 | 中国石油大学(华东) | Preparing propylene by methanol transformation silica zeolite catalyst and preparation method thereof |
| CN106140268B (en) * | 2015-04-02 | 2019-01-29 | 中国石油大学(华东) | Preparing propylene by methanol transformation total silicon molecule sieve catalyst and preparation method thereof |
| CN108940356A (en) * | 2018-05-29 | 2018-12-07 | 广东工业大学 | A kind of preparation method of Fe@ZSM-11 mesoporous molecular sieve catalyst |
| CN108940356B (en) * | 2018-05-29 | 2021-03-09 | 广东工业大学 | Preparation method of Fe @ ZSM-11 mesoporous molecular sieve catalyst |
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