CN102344329B - Method for preparing olefin by alcohol and/or ether - Google Patents
Method for preparing olefin by alcohol and/or ether Download PDFInfo
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- CN102344329B CN102344329B CN201110221537.7A CN201110221537A CN102344329B CN 102344329 B CN102344329 B CN 102344329B CN 201110221537 A CN201110221537 A CN 201110221537A CN 102344329 B CN102344329 B CN 102344329B
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Abstract
The invention provides a method suitable for preparing olefin by alcohol and/or ether, and the method comprises the following steps: firstly performing partial conversion of gaseous alcohol and/or ether raw materials in a fluidized bed reactor with a built-in heat exchanger, then allowing the partially-reacted raw material gas to enter a downstream fixed bed reactor, allowing the raw materials to be completely converted so as to prepare the required olefin product. By using the fluidized bed reactor, the temperature is uniformly distributed in the bed layer, which avoids the 'hot spot' phenomenon of the reactor, and increases the conversion rate of the raw materials. The downstream fixed bed realizes further complete conversion of unreacted raw material gas, and effectively prevents the loss of the fine powder catalyst in the fluidized bed part.
Description
Technical field
The present invention relates to the preparation method of alkene.Specifically, the present invention relates to a kind of fluidized-bed/fixed bed coupling technique that uses and by alcohol and/or ether, prepared the method for alkene.
Background technology
The low-carbon alkene that ethene, propylene is representative of take is the basic raw material in chemical industry, and along with the development of world economy, its demand increases constantly, wherein rapid with increasing of propylene demand.From 1996 to calendar year 2001, the demand growth speed of global propylene is 6.1%/year, and ethene is 4.3%/year.In general, ethene, propylene are to produce by the technique based on petroleum, but due to the limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources is constantly increasing.In recent years, people start to greatly develop the technology of being prepared ethene, propylene by alternative materials conversion.Wherein, the important alternative materials for the production of low-carbon alkene of a class is the oxygenatedchemicals of alcohol, ether and so on.By preparing propylene from methanol a kind of like this alternative techniques just, because the material benzenemethanol that this technique is used can be made by non-petroleums such as coal, Sweet natural gas, biomaterials.
At present industrializedly for the reactor by preparing propylene from methanol, mainly adopt fixed-bed reactor, for example, patent DE 10233975 has announced a kind of for the reactor by preparing propylene from methanol, contains 2-3 section beds in this reactor, and interchanger is set between every section.
In patent CN101376618, announced a kind of horizontal type fixed bed reactor, this device comprises housing, the horizontal one end of housing is provided with material inlet, the other end is provided with product outlet, in housing, be provided with porous spacing body, described porous spacing body is divided at least 4 transversely arranged regions by enclosure interior space, and two regions that are positioned at shell end are reaction zone and the cooling zone that space arranges; The corresponding housing in cooling zone is provided with cooling liquid inlet.This device reaction device project organization is simple, manufactures and keeps in repair than being easier to, easy to operate, is easy to control the reaction conditions that reaction is carried out and kept.
Because alcohol and/or ether transform the reaction of preparing alkene, it is strong exothermic process, in the fixed-bed reactor that use in prior art, if reactant flow is larger, speed of reaction is very fast, violent heat release meeting makes the temperature in technological process be difficult to keep evenly, easily the life-span of the selectivity of product, catalyzer and reactor is caused to negative impact.If reduce the flow of reactant in order to guarantee the homogeneity of temperature, can reduce the competitive power of throughput and enterprise.In addition, even carry out circulating reaction to solidifying the product stream of bed, the selectivity of target product is also often not ideal enough.The present invention proposes fluidized-bed and fixed bed to be coupled for preparing alkene by alcohol ether first, fluidized-bed carries out good control to temperature when a part of reactant is transformed, then in follow-up fixed bed, make remaining reactant transform, when improving throughput, guarantee the homogeneity of technological temperature, solved preferably the problem that prior art exists.
Summary of the invention
The invention provides a kind of fluidized-bed-fixed-bed process that adopts and by alcohol and/or ether, prepared the method for alkene, specifically comprise the following steps:
(1) fluidized-bed transforms: first described alcohol and/or ether raw material enter fluidized-bed reactor with gaseous form, contact with the catalyzer in fluidized-bed reactor, and making feedstock conversion is alkene, forms the mixture of alkene and the unreacted alcohol of part and/or ether;
(2) fixed-bed conversion: the mixture after fluidized-bed transforms enters fixed-bed reactor, contacts with the catalyzer in fixed-bed reactor, makes remaining alcohol and/or ether feedstock conversion generate olefin product.
Wherein, in fluidized-bed and fixed bed, use respectively the catalyzer that is suitable for fluidized-bed reactor and fixed-bed reactor.For example, in fluidized-bed and fixed bed, can use the ZSM-5 catalyzer of same composition, but the form of catalyzer can be different.The catalyzer that for example fluidized-bed uses can be small particle, and granularity can be 2-500 micron, preferably to 10-200 micron, and more preferably 20-200 micron, more preferably 20-100 micron; Fixed bed can be used padding and compacting to become the catalyzer of column form, and diameter can be 1-10 centimetre, and height is the right cylinder of 2-10 centimetre, and preferably diameter is 3 centimetres, and height is the right cylinder of 5-7 centimetre.
The reaction conditions of described fluidized-bed and fixed-bed conversion process can be according to factors vary such as concrete reactant, goal response speed and equipment sizes, and for example temperature of reaction is 200-600 ℃, reaction pressure 0.05-2.0Mpa, reaction velocity 0.2-6 hour
-1; Preferable reaction temperature is 420-500 ℃, and reaction pressure is 0.075-1.5MPa, and reaction velocity is 0.5-3 hour
-1.But concrete reaction conditions is not limited to above-mentioned scope, and those skilled in the art can adjust to obtain best effect to it as the case may be.
In order to promote the heat transfer process of fluidized-bed, built-in heat exchanger optionally in fluidized-bed reactor.Fixed-bed reactor comprise one or more layers catalyzer filling bed, in catalyst layer or between multi-layer catalyst filling bed, heat exchanger components are set.
Accompanying drawing explanation
Fig. 1 is for implementing the schematic diagram of fluidized-bed-fixed bed integration apparatus of the inventive method;
Fig. 2 is for implementing the schematic diagram of fluidized-bed-fixed bed self contained facility of the inventive method;
Fig. 3 is fluidized-bed-fixed bed integration apparatus that another embodiment of the present invention is used, and wherein in fluidized-bed, uses single-stage coil heat exchanger;
Fig. 4 is fluidized-bed-fixed bed integration apparatus that another embodiment of the present invention is used, and wherein in fluidized-bed, uses the U-shaped interchanger of secondary.
Embodiment
Method of the present invention adopts the reaction unit that fluidized-bed and fixed bed are coupled, in fluidized-bed, tiny beaded catalyst is dynamic suspension state under the effect of upstream, what solid catalyst particle was violent stirs up and down, heat-transfer effect has improved in the strenuous exercise of solid particulate, catalyzed reaction liberated heat is removed by the heat-transfer medium in heat exchanger apparatus rapidly, thereby reduce in time reaction bed temperature, be conducive to bed temperature equilibrium, whole reaction system is substantially in isothermal environment, bed pressure drop is low, mass transfer/heat transfer efficiency is high, reaction efficiency is fast.In fluidized-bed, make most alcohol/ether raw material reaction, for example, in the reaction of preparing propylene from methanol, after fluidized-bed step, methanol conversion can be up to 80-90%.Remaining methanol feedstock complete reaction in fixed bed, further improves methanol conversion and Propylene Selectivity, also plays in addition and catch the granules of catalyst of escaping and the effect of reclaiming heat energy from fluidized-bed.
Hereinafter, technique of the present invention is described in the reaction of mainly preparing propylene in conjunction with methyl alcohol and dme, but should be appreciated that method of the present invention can transform the reaction that prepare alkene for similar alcohol/ether.
In an embodiment of the invention, be provided with interchanger in fluidized-bed, described interchanger is selected from drift tube type interchanger, finger-type interchanger, tube exchanger and the interchanger of other structures arbitrarily.In interchanger, use heat transferring medium to promote to conduct heat.Described heat transferring medium is selected from water, thermal oil, melting salt etc.
In an embodiment of the invention, between fluidized-bed and fixed bed and the downstream of fixed bed be provided with separator, be used for solid catalyst from reactant flow.
In an embodiment of the invention, between fluidized-bed upstream and fluidized-bed and fixed bed, be provided with distribution device in gas-fluid, be used for making the air-flow that enters fluidized-bed or fixed bed to be uniformly distributed.
In an embodiment of the invention, use the coupling technique of fluidized-bed and fixed bed by preparing propylene from methanol, in fluidized-bed, catalyzer adopts ZSM-5 molecular sieve, granules of catalyst particle diameter is 20～200um, fixed bed also adopts ZSM-5 molecular sieve, adopt sheet, or cylindric or other conventional shape, further to reduce the escapement ratio of the catalyzer of fluidized-bed.This ZSM-5 is that a kind of silica alumina ratio is 200 commercial catalyst.
Fig. 1 has shown the schematic diagram of a kind of equipment that is used for implementing the inventive method.Wherein fluidized-bed and fixed bed have been taked integrated design.As we can see from the figure, gaseous feed, the mixture of methyl alcohol and water vapour for example, from the entrance access arrangement of lower end, by gas distributor 1, be uniformly distributed and come, upwards enter fluidized-bed reactor 3, in fluidized-bed reactor 3, contact with the catalyst particles of suspended state, partial reaction transforms and generates olefinic product, in order to guarantee to there is uniform and stable temperature distribution in fluidized-bed reactor 3, interchanger 2 is arranged in described fluidized-bed reactor 3, thereby heat transferring medium flows and completes heat transfer process in described interchanger 2.In fluidized-bed reactor, reacted air-flow, through gas-solid separator 4, is removed the solid catalyst carrying in air-flow, then through gas distributor 8, flows into fixed-bed reactor.At fixed-bed reactor, comprise fixed bed catalyst bed 5 and bed 7, bed 5 and 7 can comprise identical catalyzer, also can comprise the catalyzer with different size.Between bed 5 and 7, be provided with interchanger 6, be used for controlling the temperature of reaction gas flow.Through the gas delivery after fixed-bed reactor, to separating unit, reclaim target product, remove impurity.
Fig. 2 has shown the another kind of form for the equipment of the inventive method.Wherein fluidized-bed and fixed bed are respectively independently form, but the device of operating process and Fig. 1 is basic identical.By fluidized-bed and fixed bed are arranged respectively independently, make factory and enterprise in technological design, obtain greater flexibility, for example, by fluidized-bed and fixed bed are set up in parallel, can reduce the overall height of equipment, this,, for there being the situation of restriction on factory building space, is very favorable.In addition, freestanding design is also more convenient for safeguarding and installing.
Compare with fixed-bed reactor, the treatment capacity of reactor of the present invention is larger, under the condition of identical device size, can realize higher output.Specifically, fixed-bed reactor are due to the restriction of heat-sinking capability, and the flow of often having to reduce reactant, to reduce heat radiation, causes yield reducation thus.And the conversion of the most alcohol of the present invention/ether is all carried out in having the fluidized-bed of splendid thermal diffusivity, and only have the remaining alcohol/ether of small part to transform in fixed bed, therefore overcome the defect of heat radiation aspect.
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The present embodiment is used the equipment shown in Fig. 1, by preparing propylene from methanol.In this embodiment, in reaction unit of the present invention, fluidized-bed and fixed bed catalyzer used is ZSM-5 molecular sieve catalyzer, wherein fluid catalyst particle is that particle diameter is the spheroidal particle catalyzer of 50 microns, the beds 5 and 7 of fixed bed is that to be filled to diameter be 3 centimetres, and height is the cylindrical catalyst bed of 6 centimetres.
Product after reaction is sampled, adopts Agilent 7890 gas chromatographs, according to following formula, calculate reaction conversion ratio and selectivity:
Molar weight * 100% of the methyl alcohol in the molar weight/raw material of the methyl alcohol of transformation efficiency (%)=transformed
Molar weight * 100% of the methyl alcohol of the molar weight of selectivity (%)=target product/ transformed.
Reaction process by preparing propylene from methanol has below been described.
First methyl alcohol (Shanghai Wan Bang Chemical Co., Ltd., technical grade) and water are configured to the mixing raw material that molecular volume ratio is 1: 1, are heated to 400 ℃, and through gas distributor, enter fluidized-bed reactor at this temperature.In fluidized-bed reactor, there is thermopositive reaction, liberated heat is taken away by the U-shaped tubular heat exchanger in fluidized-bed, liquid water from normal temperature to heat transfer tube that input is as heat transferring medium, according to the actual temp in fluidized-bed reactor, adjust the flow of water coolant, temperature of reaction is stablized and is controlled between 420～500 ℃, this temperature regulate process is carried out with manual type in the present embodiment, but those skilled in the art are known, also can carry out temperature adjusting by the mode of automatization, reaction pressure is 0.1MPa, and methanol liquid air speed is 1.0 hours
-1, with this understanding, by vapor-phase chromatography, recording methyl alcohol reaction conversion ratio is 85%, the propylene content of generation is about 60%.Intermediate product after fluidized-bed reaction enters fixed-bed reactor through gas-solid separator 4 and gas distributor 8, and the methane in air-flow contacts and further reacts with the beds in fixed bed.Between bed, be provided with U-shaped tubular heat exchanger, wherein use equally the liquid water of room temperature as heat transferring medium, by controlling the flow of liquid water, the temperature of reaction in fixed-bed reactor is controlled to 450～490 ℃, reaction pressure is 0.1MPa, and the air speed of the methanol feedstock of Partial Conversion is 1.0 hours
-1, in exit, product stream is sampled, by vapor-phase chromatography, recording final methanol conversion is 100%, reaction product mole consists of propylene (C
3h
6): 81%, ethene (C
2h
4): 3.1%, butylene (C
4h
8): 2%, C
1-C
3lower paraffin hydrocarbons: 3%, aromatic hydrocarbons: 4%, surplus is C
5, C
6deng high-carbon hydrocarbon, CO
2, CO etc.
Embodiment 2
The present embodiment is used the equipment shown in Fig. 2, according to raw material and reaction conditions described in embodiment 1, reacts, and in fluidized-bed, reacted mixture shows that methyl alcohol reaction conversion ratio is 83.5%, and the propylene content of generation is about 59%.Methanol conversion in final reacting product is 100%, mole consists of propylene (C
3h
6): 79%, ethene (C
2h
4): 3%, butylene (C
4h
8): 1.9%, C
1-C
3lower paraffin hydrocarbons: 3.2%, aromatic hydrocarbons: 4%, surplus is C
5, C
6deng high-carbon hydrocarbon, CO
2, CO etc.
Embodiment 3
The present embodiment adopts the process identical with embodiment 1, and difference is to use dme as raw material.In fluidized-bed, reacted mixture shows that dme reaction conversion ratio is 75.6%, and the propylene content of generation is about 51.2%.Dimethyl ether conversion rate in final reacting product is 97.6%, mole consists of propylene (C
3h
6): 70.1%, ethene (C
2h
4): 8.2%, butylene (C
4h
8): 2.9%, C
1-C
3lower paraffin hydrocarbons: 4.6%, aromatic hydrocarbons: 4.5%, surplus is C
5, C
6deng high-carbon hydrocarbon, CO
2, CO etc.
Embodiment 4
The present embodiment adopts the process identical with embodiment 1, and difference is, uses single-stage coil heat exchanger to replace U-shaped tubular heat exchanger in fluidized-bed, and conversion unit as shown in Figure 3.In fluidized-bed, reacted mixture shows that methyl alcohol reaction conversion ratio is 88%, and the propylene content of generation is about 64%.Reaction product mole consists of propylene (C
3h
6): 84%, ethene (C
2h
4): 3.3%, butylene (C
4h
8): 2.5%, C
1-C
3lower paraffin hydrocarbons: 4%, aromatic hydrocarbons: 4%, surplus is C
5, C
6deng high-carbon hydrocarbon, CO
2, CO etc.As can be seen here, coil heat exchanger due to fluidized-bed in material contact area larger, can control better the consistence of the temperature in fluidized-bed reactor, can further improve technique transformation efficiency and selectivity thus.
Embodiment 5
The present embodiment adopts the process identical with embodiment 1, and difference is, uses secondary U-shaped tubular heat exchanger to replace the single-stage U-shaped tubular heat exchanger of embodiment 1 in fluidized-bed, and conversion unit as shown in Figure 4.In fluidized-bed, reacted mixture shows that methyl alcohol reaction conversion ratio is 87%, and the propylene content of generation is about 62.5%.Reaction product mole consists of propylene (C
3h
6): 82.5%, ethene (C
2h
4): 3.5%, butylene (C
4h
8): 3%, C
1-C
3lower paraffin hydrocarbons: 4%, aromatic hydrocarbons: 4.5%, surplus is C
5, C
6deng high-carbon hydrocarbon, CO
2, CO etc.As can be seen here, the material contact area in 2 grades of U-shaped interchanger and fluidized-bed is larger, can control better the consistence of the temperature in fluidized-bed reactor, can further improve technique transformation efficiency and selectivity thus.
Comparative example 1
In the situation that only use the fixed bed device shown in Fig. 2, adopt raw material and the processing condition identical with embodiment 1 to react, after reaction starts, even the water temperature in interchanger is adjusted to minimum, temperature in fixed-bed reactor is still increased to very soon over 530 ℃, the transformation efficiency of methyl alcohol is only 38%, and propylene content is less than 19%.
As can be seen here, this comparative example is compared with embodiment 1, and it is poor that its temperature is controlled, and catalyst deactivation is fast, and methanol conversion is low.If reach high conversion and temperature control preferably, must in each beds, adopt multi-stage heat exchanger to strengthen heat exchange, and augmenting response device size.Adopt fluidized-bed and the mode of the coupling of fixed bed can realize splendid temperature control, follow-up fixed-bed reactor simplicity of design, can, further by methane conversion, significantly improve output.
In addition, from embodiment 1, through fluidized-bed reaction, being not yet cured a data for the product of reaction can see, if use separately fluidized-bed to carry out the reaction that methanol conversion is propylene, raw material once cannot meet the demands through the transformation efficiency after fluidized-bed.In the situation that the fixed bed unit after not comprising, the product that those skilled in the art obtain fluidized-bed exit by having to is even repeatedly recycled to again fluidized-bed entrance and reacts to obtain required high conversion, has greatly improved thus process complexity, cycle time and running cost.Form therewith sharp contrast, in the present invention, only by fluidized-bed once, the fixed bed by downstream makes remaining reactant reaction complete to raw material subsequently, because design operation and the maintenance of fixed bed are all more easy, has greatly simplified production technique.
Claims (7)
1. by a method for preparing propylene from methanol, the method is included in the reactor assembly being comprised of with fixed bed coupling fluidized-bed is reacted and prepares propylene under gaseous state condition by methyl alcohol, and it specifically comprises the following steps:
(1) fluidized-bed transforms: make methanol feedstock enter fluidized-bed reactor with gas form, contact with the catalyzer in fluidized-bed reactor, dehydration reaction occurs, obtain the mixture of propylene and the unreacted methyl alcohol of part, in its Raw, methyl alcohol is 1:1 with the molecular volume ratio of water; Fluidized-bed step of converting use granularity is the spherical particle ZSM-5 catalyzer of 20～200 microns;
(2) fixed-bed conversion: the mixture obtaining after fluidized-bed is transformed enters fixed-bed reactor, contacts with the catalyzer in fixed-bed reactor, makes remaining methanol feedstock transform generation propylene completely; It is 1-10 centimetre that fixed-bed conversion step is used diameter, and height is the cylindric ZSM-5 catalyzer of 2-10 centimetre.
2. the method for claim 1, is characterized in that, the temperature of reaction of described fluidized-bed step of converting is 200-600 ℃, reaction pressure 0.05-2.0MPa, reaction velocity 0.2-6h
-1; The temperature of reaction of described fixed-bed conversion step is 200-600 ℃, reaction pressure 0.05-2.0MPa, reaction velocity 0.2-6h
-1.
3. the method for claim 1, is characterized in that, built-in heat exchanger in described fluidized-bed reactor, and described built-in interchanger comprises serpentine heat exchanger, U-shaped tubular heat exchanger or shell and tube heat exchanger.
4. the method for claim 1, is characterized in that, described fixed-bed reactor comprise one or more layers catalyzer filling bed, in described catalyzer packing layer or between multi-layer catalyst filling bed, heat-exchanger rig is set.
5. the method for claim 1, is characterized in that, described in step (1), the granularity of spherical particle ZSM-5 catalyzer is 20-100 micron; Described in step (2), the diameter of cylindric ZSM-5 catalyzer is 3 centimetres, and height is 5-7 centimetre.
6. the method for claim 1, is characterized in that, between fluidized-bed and fixed bed and the downstream of fixed bed be provided with separator, be used for solid catalyst from reactant flow.
7. the method for claim 1, is characterized in that, between fluidized-bed upstream and fluidized-bed and fixed bed, is provided with distribution device in gas-fluid, is used for making the air-flow that enters fluidized-bed or fixed bed to be uniformly distributed.
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| MY170027A (en) * | 2012-08-10 | 2019-06-25 | Asahi Kasei Chemicals Corp | Method for converting olefin or alcohol and method for producing propylene or aromatic compound |
| CN104107671B (en) * | 2013-04-18 | 2017-04-05 | 上海碧科清洁能源技术有限公司 | Fluidized-bed reactor and the method for carrying out methanol to olefins reaction with the fluidized-bed reactor |
| CN104843648A (en) * | 2015-06-02 | 2015-08-19 | 傅骐 | Fixed bed hydrogenation reaction system for preparing hydrogen peroxide by using anthraquinone process |
| CN106008126B (en) * | 2016-05-20 | 2018-08-10 | 四川金象赛瑞化工股份有限公司 | A kind of method and system of methanol hydrocarbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0099650A1 (en) * | 1982-07-20 | 1984-02-01 | Mobil Oil Corporation | Two-stage, zeolite catalyzed process for the conversion of alcohols to hydrocarbons |
| CN101165022A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propylene |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0099650A1 (en) * | 1982-07-20 | 1984-02-01 | Mobil Oil Corporation | Two-stage, zeolite catalyzed process for the conversion of alcohols to hydrocarbons |
| CN101165022A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propylene |
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