CN103894222B - For the modified zeolite catalyst and preparation method thereof of methanol dewatered propylene - Google Patents
For the modified zeolite catalyst and preparation method thereof of methanol dewatered propylene Download PDFInfo
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- CN103894222B CN103894222B CN201210588048.XA CN201210588048A CN103894222B CN 103894222 B CN103894222 B CN 103894222B CN 201210588048 A CN201210588048 A CN 201210588048A CN 103894222 B CN103894222 B CN 103894222B
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Abstract
The present invention discloses the Catalysts and its preparation method that a kind of modified ZSM-5 zeolite is used for preparing propylene from methanol catalytic reaction, and this catalyst is based on total silicon ZSM-5 zeolite, by aluminium atom hybrid modification, introduces controlled acid site and is formed.This acidity of catalyst is moderate, is particularly conducive to methanol conversion, and high selectivity produces propylene.This catalyst activity is good, and reaction conversion ratio is high, and stable period is long.With mass concentration 30-100% methyl alcohol for reaction raw materials, single pass life is greater than 800 hours, and Propylene Selectivity is greater than 48%, and renovation process is simple, and regenerability recovers good.
Description
Technical field
The present invention relates to industrial circle, relate to a kind of Catalysts and its preparation method of methanol dewatered propylene specifically.
Background technology
Zeolite molecular sieve is a kind of inorganic silicon aluminate crystal, containing the regular and duct (ca.0.3-1.5nm) of the molecular dimension of ordered arrangement in skeleton, 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 be most widely used up to now, be widely used in petroleum streams fluidized catalytic cracking (FCC), hydrocracking and in the oil refining process such as refining.Also numerous important application is had at the catalytic field of petrochemical industry, fine chemistry industry and environmental protection etc.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, and surface has stronger acidity, usually has higher activity and selectivity to product.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 process, 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, form skeleton defect, the catalyst made is easy coking in catalytic reaction, thus reduces the stability of its activity.And regenerate frequently, its skeleton structure can be destroyed, 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), the core technology with ICL for Indirect Coal Liquefaction alkene and bio-ethanol alkene petroleum replacing route in current non-petroleum technology, strategic importance and using value 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 selective higher.In MTP reaction, the advantage [the open CN101269340A of patent] of high Propylene Selectivity and high propylene/ethylene ratio is shown at the ZSM-5 zeolite catalyst using binder free technology to prepare, but continuous print catalytic reaction products yield easily fluctuates, less stable.
Therefore, there is the demand of the Catalysts and its preparation method for methanol dewatered propylene that performance is improved at present.
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 additionally provides the preparation method of this catalyst.Another object of the present invention there is provided the renovation process of described catalyst.In addition, the present invention also aims to the application that this catalyst is provided.
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, not containing aluminium element;
ZSM-5 zeolite, through Metal aluminum 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 with Alumina gel is the method that above-mentioned catalyst prepared by binding agent, and 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 working solution concentration represents with Al ion molar concentration, the preferred 0.05-1mol/L of concentration.
Mixed with aluminium salt working solution by zeolite, wherein the weight ratio of zeolitic material and aluminium salt working solution is 1:2-1:10.
Be positioned in autoclave after being mixed with aluminium salt working solution by zeolite, add thermal response after airtight in baking oven, wherein reaction temperature is 100-200 DEG C, and the heat time is 12-48 hour.
Reaction completes, and is taken out by mixture from reactor, in 90-120 DEG C of oven for drying.
Solid sample after drying is placed in 300-550 DEG C of Muffle furnace roasting 1-10 hour.
ZSM-5 zeolite catalyst, after aluminium is atom modified, wherein containing four-coordination framework aluminum, the framework aluminum of pentacoordinate and the non-framework aluminum of hexa-coordinate.
In addition, described catalyst can also be regenerated by the method comprised the following steps:
Control beds 300-350 DEG C, with 5%-10%O
2(N
2for carrier gas) 10-50mL/min purges 1-5 hour; Be warmed up to 400-450 DEG C, with 5%-20%O
2(N
2for carrier gas) 10-50mL/min purges 1-5 hour; Be warmed up to 500-550 DEG C, 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 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 (
27alNMR).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 strength 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 process, 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, form skeleton defect, the catalyst made is easy coking in catalytic reaction, thus reduces the stability of its activity.And regenerate frequently, its skeleton structure can be destroyed, 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 proves, atom modified through aluminium, 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 application of the present invention reacts in MTP, and catalytic activity, methyl alcohol average conversion and Propylene Selectivity are high, and the stable period of catalytic reaction high conversion is long, and methanol conversion decay is slow, keeps the time of more than 98% conversion ratio long.
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.With mass concentration 30-100% methyl alcohol for reaction raw materials, single pass life is greater than 800 hours, and Propylene Selectivity is greater than 48%, and renovation process is simple, and regenerability recovers good.
Accompanying drawing explanation
Below, describe embodiments of the invention in detail by reference to the accompanying drawings, 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.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further, but these embodiments are only limitted to explain the present invention, and are not used in restriction the present invention.The experimental technique of not marked specific experiment condition in embodiment below, usually conveniently condition, or according to the condition that manufacturer advises, the change of technical scheme is all in protection scope of the present invention in the examples below.
embodiment 1-9: the preparation of aluminium salt working solution
Prepare typical feedstock that aluminium salt working solution adopts and proportioning, preparation condition etc. see the following form 1.
The preparation of table 1, aluminium salt working solution
Preparation process is as follows:
For embodiment 1, take 17.1 grams, anhydrous slufuric acid aluminium, import beaker, add suitable quantity of water and dissolve, pour 1L volumetric flask into after dissolving completely, be settled to 1L.
embodiment 10-18: catalyst hydrothermal modification
2 are seen the following form 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:
For embodiment 12, take 100 grams dry, ZSM-5 zeolite powder (Shanghai Fuxu Molecular Sieve Co., Ltd.), move into beaker, the working solution 300 grams taking embodiment 2 configuration pours above-mentioned beaker into, stirs evenly rear stand-by.
embodiment 19: catalyst preparing completes and performance evaluation
Mixture embodiment 12 obtained moves into the autoclave of 500mL, 24 hours are heated after sealing with 180 DEG C of baking ovens, mixture in still is poured into crucible after reaction terminates, be positioned over 100 DEG C of oven for drying moisture, proceed to 550 DEG C of Muffle furnace roastings 5 hours again, obtain the catalyst prepared.
Analyze the physico-chemical property of obtained catalyst and catalytic performance, result is as follows:
Fig. 1 is the XRD spectra of catalyst.Can find out that this catalyst is typical MFI structure types of molecules 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, do not form other crystal structure.
27the co-ordination state of AlNMR analysis result display Al, based on four-coordination, 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-bound 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 surface area and total hole volume are respectively 360m
2/ g and 0.25cm
3/ g, illustrates its perfect structure and duct is open.
Fig. 2 is the NH of catalyst
3-TPD spectrogram.Desorption peaks near 280 DEG C is wanted obviously move to high temperature direction compared with the desorption peaks corresponding to weak acid position near 200 DEG C, total silicon ZSM--5 zeolite, illustrates and to be enhanced with the faintly acid of Alumina gel moulded zeolite catalyst; Meanwhile, occur a large Bao Feng, and have no obvious high-temperature strong acid position desorption peaks, the acid site occurring a large amount of moderate strengths is described in catalyst 400-800 DEG C of scope, the desorption peaks that corresponding desorption peaks is corresponding with strong acid center forms overlap and cannot separate.But it is less still to show as weak acid center in the Acidity of entirety, and strong acid center is many, there is the characteristic in a certain amount of moderate strength acid site.
embodiment 20: the catalytic effect examination of catalyst
Catalyst 120g embodiment 18 prepared loads in fixed bed reactors, with the industrial methanol of mass concentration 90% for raw material, and mass space velocity 1h during methanol solution
-1, under 480 DEG C of reaction temperatures, carry out catalysis examination.Methyl alcohol average conversion is more than 98% in 800 hours for this catalyst, and its active maintenance stablizes; Ethene average selectivity is about 6.8%, and propylene average selectivity is 48.6%.
embodiment 21: the regeneration of catalyst
After the catalytic reaction stopping of embodiment 20, control beds 350 DEG C, with 5%O
2(95%N
2) 20mL/min purges 2 hours; Be warmed up to 450 DEG C, with 5%O
2(95%N
2) 20mL/min purges 2 hours; Be warmed up to 550 DEG C, with 10%O
2(90%N
2) 20mL/min purges 2 hours, 10%O
2(90%N
2) 50mL/min purges 5 hours, carries out regeneration process to catalyst.
embodiment 22: the catalytic effect examination of catalyst regeneration
After embodiment 21 regeneration ending, control temperature of reactor 480 DEG C, with the industrial methanol of mass concentration 90% for raw material, mass space velocity 1h during methanol solution
-1again carry out catalytic evaluation, catalyst activity recovers substantially completely, in 600 hours, still keep methyl alcohol average conversion more than 99%, ethene average selectivity 7.2%, propylene average selectivity 48.5%.Catalytic reaction result and fresh catalyst reaction result basically identical, illustrate through regeneration process catalyst activity recover completely.
Claims (3)
1. the zeolite catalyst for methanol dewatered propylene, it is characterized in that this zeolite catalyst is using total silicon zeolite as substrate, formed through aluminium atom hydridization, the preparation method of described zeolite catalyst is: ZSM-5 zeolite is through Metal aluminum salt solution impregnation, heat in closed reactor again, take out post-drying, after high-temperature roasting, obtain ZSM-5 zeolite catalyst.
2. the zeolite catalyst for methanol dewatered propylene according to claim 1, is characterized in that described zeolite is ZSM-5 zeolite, the skeleton SiO of the described zeolite catalyst prepared
2/ Al
2o
3scope is at 100-1000.
3. prepare a method for zeolite catalyst described in claim 1 or 2, it is characterized in that the method is:
Mixed with aluminium salt working solution by zeolite, be positioned in autoclave, add thermal response after airtight in baking oven, wherein reaction temperature is 100-200 DEG C, and the heat time is 12-48 hour;
Reaction completes, and is taken out by mixture from reactor, in 90-120 DEG C of oven for drying;
Solid after drying is placed in 300-550 DEG C 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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| 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 |
| CN108940356B (en) * | 2018-05-29 | 2021-03-09 | 广东工业大学 | Preparation method of Fe @ ZSM-11 mesoporous molecular sieve catalyst |
Citations (3)
| 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 |
| 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 |
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| KR101394625B1 (en) * | 2007-06-25 | 2014-05-13 | 에스케이이노베이션 주식회사 | Preparation Method of the Zeolite containing Iron catalyst for SCR(Selective catalyst reaction) |
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Patent Citations (3)
| 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 |
| 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 |
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