CN101406846A - Catalyst for preparing propylene from methanol or dimethyl ether and method of use thereof - Google Patents
Catalyst for preparing propylene from methanol or dimethyl ether and method of use thereof Download PDFInfo
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- CN101406846A CN101406846A CNA200810203275XA CN200810203275A CN101406846A CN 101406846 A CN101406846 A CN 101406846A CN A200810203275X A CNA200810203275X A CN A200810203275XA CN 200810203275 A CN200810203275 A CN 200810203275A CN 101406846 A CN101406846 A CN 101406846A
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- catalyst
- dimethyl ether
- propylene
- molecular sieve
- methyl alcohol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a catalyst for preparing propylene by using methanol or dimethyl ether, as well as an application method thereof. The catalyst consists of an HZSM-5 molecular sieve with the grain size of between 20 and 100 nanometers and a binding agent, wherein the weight percentage content of the HZSM-5 molecular sieve is between 40 and 90 percent; the weight percentage content of the binding agent is between 10 and 60 percent; and the binding agent is selected from SiO2, Al2O3 and clay or a mixture of more than one of the three. When the catalyst is used, the methanol or the dimethyl ether is used as a raw material, and the mixture of the raw material and water as a thinner contacts and reacts with the catalyst to form effluent containing the propylene. The catalyst used for preparing propylene through the methanol or the dimethyl ether has higher propylene yield and catalyst stability.
Description
Technical field
The present invention relates to a kind of novel ZSM-5 molecular sieve catalyst and using method thereof that is used for methyl alcohol or dimethyl ether production propylene.
Background technology
Propylene is a kind of important basic organic, is mainly used in chemical products such as producing polypropylene, acrylonitrile and expoxy propane.The production of propylene and series of products thereof, consumption and development and national economy are closely related, and the supply of propylene has also embodied the strength of a national chemical industry.At present, propylene is mainly from the catalytic cracking unit of preparing ethylene by steam cracking device and oil refining.Because oil is non-renewable resources, reserves are very limited, and the price of oil rises steadily, so countries in the world begin to be devoted to the exploitation of non-petroleum path system propylene technology.Wherein, receive more and more widely concern by the technology of coal and natural gas via methyl alcohol or dimethyl ether system propylene (MTP).The key of MTP technology is the development of high performance catalyst, at present, to the MTP reacting catalytic performance best surely belong to the HZSM-5 molecular sieve.Under the effect of catalyst, methyl alcohol at first dewaters and generates dimethyl ether (DME), and the equilibrium mixture of DME and methyl alcohol continues to be converted into the low-carbon alkene based on ethene and propylene then.The low-carbon alkene that is generated further generates alkane, aromatic hydrocarbons and higher olefins by reactions such as polycondensation, cyclisation, dehydrogenation, alkylation and hydrogen migrations.Therefore, for the selectivity that improves propylene can be taked to improve the methyl alcohol air speed and use diluted methyl alcohol as reactant, to shorten the time of staying of propylene at catalyst surface.But two kinds of methods all can cause the significant wastage of energy consumption, thereby the production cost of propylene is significantly increased.And adopt the less ZSM-5 molecular sieve of crystallite dimension can shorten the time of staying of propylene equally, thereby improve the selectivity of propylene at catalyst surface.As document (petrochemical industry, 1983,12 (9): 531) find that crystallite dimension is that all to be higher than crystallite dimension be 3～5 microns ZSM-5 molecular sieve for 0.5 micron the propylene selectivity of ZSM-5 molecular sieve and propylene/ethylene quality.Document (catalysis journal, 1983,4 (3): 248) reported that crystallite dimension be that the propylene selectivity (36.1%) of 0.25～0.5 micron ZSM-5 molecular sieve catalyst wants obviously be 3～4 microns ZSM-5 molecular sieve catalyst (21.5%) greater than crystallite dimension.Document (Chemical Reaction Engineering and technology, 2007,23 (6): 481) prepared four kinds of ZSM-5 molecular sieve catalysts that grain size is respectively 0.6,2,10 and 20 micron, the MTP reaction result shows reducing with the zeolite crystal size, the yield of propylene increases gradually, and peak has reached 44.1%.But owing to existing be used for methyl alcohol or dimethyl ether system propylene catalyst for reaction all adopts the bigger micron order ZSM-5 molecular sieve of crystal grain, so exist propene yield to hang down shortcoming with poor stability.
Summary of the invention
Technical problem to be solved by this invention provides the novel ZSM-5 molecular sieve catalyst and the using method thereof that are used for methyl alcohol or dimethyl ether production propylene that a kind of catalyst stability is better, propene yield is higher.
Technical solution of the present invention: a kind of catalyst that is used for methyl alcohol or dimethyl ether production propylene, formed by the HZSM-5 molecular sieve and the binding agent of 20～100 nanometers by crystallite dimension, wherein the quality percentage composition of HZSM-5 molecular sieve is 40～90%, the quality percentage composition of binding agent is 10～60%, and described binding agent is selected from SiO
2, Al
2O
3, one or more the mixture in the clay.
The using method of above-mentioned catalyst is a raw material when using described Preparation of Catalyst propylene with methyl alcohol or dimethyl ether, is diluent with water, and the mixture of raw material and diluent is generated the effluent that contains propylene with the catalyst reaction that contacts.
Reaction temperature is 400～550 ℃ when using catalyst.
The air speed of material benzenemethanol or dimethyl ether is 0.2～10h when using catalyst
-1
The mass ratio of methyl alcohol or dimethyl ether and water is 0.2～5: 1 when using catalyst.
Beneficial effect of the present invention: methanol molecules participates in reaction by the inner surface that diffusion enters into molecular sieve.If the crystallite dimension of molecular sieve is too big, methanol molecules is subjected to certain resistance, the inner surface to molecular sieve more difficult to get access, and can only participate in reaction at the outer surface of molecular sieve, thus reduced the surperficial utilization rate of molecular sieve.In addition, if the crystallite dimension of molecular sieve is too big, the path that the propylene that generated of reaction diffuses out in the molecule sieve aperture is longer, the time of staying on molecular sieve is also longer, further reaction generates accessory substances such as alkane, aromatic hydrocarbons and higher olefins, not only reduced propene yield, also made the catalyst rapid deactivation.Nano molecular sieve (crystallite dimension is less than 100nm) is because of having very little crystallite dimension and very big specific area, characteristics such as show more than the short and surface acid center quantity of tangible diffusion distance, thereby have catalytic activity height, carbon deposit is few and carbon accumulation resisting ability is strong remarkable advantage.The central principle of the inventive method is to adopt the catalyst of nano-ZSM-5 molecular sieve preparation by methyl alcohol or dimethyl ether conversion system propylene, therefore have the advantage of methyl alcohol or dimethyl ether conversion rate and propylene selectivity height and good stability, effectively overcome and be used for the low shortcoming with poor stability of methyl alcohol or the existing propylene selectivity of dimethyl ether conversion system propylene catalyst for reaction in the prior art.
The specific embodiment
Below by embodiment and comparing embodiment the present invention is described in further detail, a kind of catalyst that is used for methyl alcohol or dimethyl ether production propylene, formed by the HZSM-5 molecular sieve and the binding agent of 20～100 nanometers by crystallite dimension, wherein the quality percentage composition of HZSM-5 molecular sieve is 40～90%, the quality percentage composition of binding agent is 10～60%, and described binding agent is selected from SiO
2, Al
2O
3, one or more the mixture in the clay.
The using method of above-mentioned catalyst is a raw material when using described Preparation of Catalyst propylene with methyl alcohol or dimethyl ether, is diluent with water, and the mixture of raw material and diluent is generated the effluent that contains propylene with the catalyst reaction that contacts.Reaction temperature is 400～550 ℃ when using catalyst.The air speed of material benzenemethanol or dimethyl ether is 0.2～10h when using catalyst
-1The mass ratio of methyl alcohol or dimethyl ether and water is 0.2～5: 1 when using catalyst.
The catalyst of the present invention preparation can be used for fixed bed reactors and also can be applicable to fluidized-bed reactor, both can methyl alcohol or dimethyl ether be raw material, also can methyl alcohol and the mixture of dimethyl ether be raw material.
An example of the inventive method of using fixed bed reactors is hereinafter described.It is 6mm that a certain amount of catalyst granules (20～40 order) is loaded in internal diameter, and length is in the stainless steel reactor of 300mm.Adopt electrical heating, temperature is controlled automatically.Reactor bottom filling 20～40 purpose inert materials are as supporter, and filling 20～40 purpose inert materials in catalyst top are made for the usefulness of raw material preheating.By beds, raw material is a methyl alcohol to raw material from top to bottom, and water is diluent, and the mass ratio of methyl alcohol and water is 0.3: 1; The air speed of methyl alcohol is 1h
-1Reaction pressure is that normal pressure, temperature are 500 ℃.The 6820 type gas chromatographs that product adopts Agilent company to produce carry out on-line analysis.
[embodiment 1]
With 2 gram crystallite dimensions is the HZSM-5 molecular sieve and the 1 gram Al of 50～80 nanometers
2O
3Binding agent mixes mutually, obtains catalyst A in 8 hours 600 ℃ of following roastings then.
[embodiment 2～4]
1 gram catalyst A is packed in the fixed bed reactors, and (30 ml/min) temperature to 500 that raises gradually ℃ under stream of nitrogen gas kept after 1 hour, nitrogen was switched to the mixture (mass ratio of methyl alcohol and water is 0.3: 1) of methyl alcohol and water; The charging rate of methyl alcohol is 1 Grams Per Hour; Reaction temperature is respectively 450,500 and 520 ℃.Take a sample after 4～6 hours when reaction, the 6820 type gas chromatographs that adopt Agilent company to produce carry out on-line analysis, the results are shown in Table 1.
[embodiment 5～6]
With embodiment 2～4, just the charging rate of methyl alcohol is respectively 2 Grams Per Hours and 4 Grams Per Hours, and reaction temperature is 500 ℃.The results are shown in Table 1.
[embodiment 7～8]
With embodiment 2～4, just the mass ratio of methyl alcohol and water was respectively 0.5: 1 and 1: 1, and reaction temperature is 500 ℃.The results are shown in Table 1.
[embodiment 9]
With embodiment 2～4, just reaction temperature is 500 ℃, reacts for a long time to investigate the stability of catalyst.The results are shown in Table 2.
[comparative example 1]
With embodiment 1, just adopting crystallite dimension is that 3～5 microns HZSM-5 molecular sieve prepares catalyst B.
[comparative example 2]
The method of employing embodiment 9 comments the reactivity worth of valency catalyst B, the results are shown in Table 2.
The reactivity worth of table 1 catalyst
The test of table 2 life of catalyst
By data in the table as seen, adopt the catalyst and the using method thereof of the inventive method,, have very high propene yield and stability for the preparing propylene by methanol transformation reaction.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. catalyst that is used for methyl alcohol or dimethyl ether production propylene, formed by the HZSM-5 molecular sieve and the binding agent of 20～100 nanometers by crystallite dimension, wherein the quality percentage composition of HZSM-5 molecular sieve is 40～90%, the quality percentage composition of binding agent is 10～60%, and described binding agent is selected from SiO
2, Al
2O
3, one or more the mixture in the clay.
2. the using method of the described catalyst of claim 1 is a raw material when using described Preparation of Catalyst propylene with methyl alcohol or dimethyl ether, is diluent with water, and the mixture of raw material and diluent is generated the effluent that contains propylene with the catalyst reaction that contacts.
3. catalyst using method according to claim 2 is characterized in that: reaction temperature is 400～550 ℃.
4. catalyst using method according to claim 2 is characterized in that: the air speed of material benzenemethanol or dimethyl ether is 0.2～10h
-1
5. catalyst using method according to claim 2 is characterized in that: the mass ratio of methyl alcohol or dimethyl ether and water is 0.2～5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810203275XA CN101406846A (en) | 2008-11-25 | 2008-11-25 | Catalyst for preparing propylene from methanol or dimethyl ether and method of use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810203275XA CN101406846A (en) | 2008-11-25 | 2008-11-25 | Catalyst for preparing propylene from methanol or dimethyl ether and method of use thereof |
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| CN101406846A true CN101406846A (en) | 2009-04-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011159202A1 (en) * | 2010-06-17 | 2011-12-22 | Учреждение Российской Академии Наук Ордена Трудового Красного Знамени Институт Нефтехимического Синтеза Им А.В. Топчиева Ран (Инхс Ран) | Catalyst and method for producing olefins from dimethyl ether in the presence of said catalyst |
| CN103030499A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing propylene through conversion of methanol |
| CN116408134A (en) * | 2021-12-30 | 2023-07-11 | 卓悦环保新材料（上海）有限公司 | Anti-crushing catalyst for preparing propylene from methanol, and preparation method and application thereof |
-
2008
- 2008-11-25 CN CNA200810203275XA patent/CN101406846A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011159202A1 (en) * | 2010-06-17 | 2011-12-22 | Учреждение Российской Академии Наук Ордена Трудового Красного Знамени Институт Нефтехимического Синтеза Им А.В. Топчиева Ран (Инхс Ран) | Catalyst and method for producing olefins from dimethyl ether in the presence of said catalyst |
| RU2445158C2 (en) * | 2010-06-17 | 2012-03-20 | Учреждение Российской Академии Наук Ордена Трудового Красного Знамени Институт Нефтехимического Синтеза Им. А.В. Топчиева Ран (Инхс Ран) | Catalyst and method of producing olefins from dimethyl ether in its presence |
| CN103030499A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing propylene through conversion of methanol |
| CN103030499B (en) * | 2011-09-29 | 2014-11-26 | 中国石油化工股份有限公司 | Method for preparing propylene through conversion of methanol |
| CN116408134A (en) * | 2021-12-30 | 2023-07-11 | 卓悦环保新材料（上海）有限公司 | Anti-crushing catalyst for preparing propylene from methanol, and preparation method and application thereof |
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Open date: 20090415 |