CN1259294C - Improved method for producing styrene by ethyl benzene catalyzed dehydrogenation - Google Patents
Improved method for producing styrene by ethyl benzene catalyzed dehydrogenation Download PDFInfo
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- CN1259294C CN1259294C CN 200410052662 CN200410052662A CN1259294C CN 1259294 C CN1259294 C CN 1259294C CN 200410052662 CN200410052662 CN 200410052662 CN 200410052662 A CN200410052662 A CN 200410052662A CN 1259294 C CN1259294 C CN 1259294C
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Abstract
The present invention discloses an improvement method for preparing styrene from ethylbenzene catalytic dehydrogenation, which is characterized in that steam heats reaction effluents through a heat exchanger in a first stage and is divided into two strands in a second stage. The main body steam of the steam is mixed with ethylbenzene at the ingress of a first dehydrogenation reactor, and the mass ration of the steam to the ethylbenzene is 0.6 to 1.4: 1. The other strand complementary steam is mixed with exit matedial of the first dehydrogenation reactor at the ingress of a second dehydrogenation reator, and the mass ratio of the total of steam of a reaction system to the ethylbenzene is 1.2 to 1.8: 1. Compared with the prior art, the present invention has the maximum advantages of reducing the pressure drop of a reaction system and decreasing equipment investment.
Description
Technical field
The present invention relates to a kind of in the presence of steam the method with producing phenyl ethylene by ethyl benzene catalytic dehydrogenation.
Background technology
Vinylbenzene is widely used as production various kinds of resin, plastics and elastomeric raw material, extensively mainly being easy to polymerization (for example generating polystyrene) owing to vinylbenzene or carrying out the adaptability of copolymerization (for example producing rubber with butadiene copolymer) of its range of application.
(application number: disclose a kind of process for manufacturing styrene 87102929), its dehydrogenation comprises in three placed in-line fixed bed dehydrogenation reactors at a cover carries out document CN1006061B, settles one or more interchanger between reactor.In interchanger, reaction mass and high-temperature steam generation heat exchange and be heated, high-temperature steam is used for the reacting by heating effluent in the fs, mix with ethylbenzene in the first dehydrogenation reactor ingress in subordinate phase, the conversion of ethylbenzene of three sections middle heat-exchanging process of negative pressure adiabatic reaction is about 70～78%, and selectivity can be greater than 94%.This processing method adopts a plurality of heat-exchange equipments and process furnace, and facility investment is big, also causes system pressure drop to increase in addition, influences reactivity worth.
Summary of the invention
The facility investment that the present invention is directed to the middle existence of prior art (technology that patent documentation CN1006061B is reported) reaches the big defective of system pressure drop greatly and proposes following technical scheme:
Technical scheme:
The method of the said producing phenyl ethylene by ethyl benzene catalytic dehydrogenation of the present invention, it adopts multistage composite heat-exchange reaction process, dehydrogenation comprises in three placed in-line dehydrogenation reactors at a cover at least carries out, settle a heat-exchanger rig before each reactor, reaction mass and high-temperature water vapor are through directly or indirectly entering reactor after the heat exchange, reaction mass is heated to 550～650 ℃ in each dehydrogenation reactor ingress, absolute pressure mean value in first reactor is 0.05～0.10Mpa, second and remain between 0.03～0.08Mpa with the absolute pressure mean value in the post-reactor, liquid ethylbenzene cumulative volume air speed is 0.25～0.4 hour
-1Material after the dehydrogenation reaction carries out flowing into product separation system after heat is reclaimed in heat exchange through interchanger, after separating, get product, it is characterized in that, water vapor comes the reacting by heating effluent in the fs by interchanger, and be divided into two strands in subordinate phase, its main body water vapor mixes with ethylbenzene in the ingress of first dehydrogenation reactor, the mass ratio of water vapor and ethylbenzene is 0.6～1.4: 1, another burst make up water steam mixes with the first dehydrogenation reactor outlet material in the ingress of second dehydrogenation reactor, and the steam that reactive system is total and the mass ratio of ethylbenzene are 1.2～1.8: 1.
The catalyzer of Cai Yonging is the existing catalyzer based on ferric oxide that is used for ethylbenzene dehydrogenation in the present invention.Any dehydrogenation reactor all can be used to implement method of the present invention, but is advisable with radial reactor or axial-radial flow reactor.The ratio of main water vapor and make up water steam preferred 0.5～4: 1 (mass ratio).
The present invention has the following advantages:
The one, equipment is simple, less investment, and existing relatively ethylbenzene negative dehydrogenation three segment process have reduced by an interchanger, have saved investment; The 2nd, according to the requirement of reaction, segmentation is mended into steam, adapts to the characteristics of multistage reaction, can reduce system pressure drop (can reduce by 2～3kPa, at same catalyst) again; The 3rd, adopt direct heat exchange to substitute indirect heat exchange, then pressure drop is little, more meets the ethylbenzene dehydrogenation negative-pressure operation; The 4th, conversion of ethylbenzene height, conversion of ethylbenzene are 70～78%, and selectivity is about 95% or higher, and the utilization ratio of heat is than two step process height, and simultaneously corresponding minimizing is the load of system's separating device afterwards.
Description of drawings
Fig. 1 is the schematic flow sheet of producing phenyl ethylene by ethyl benzene catalytic dehydrogenation method of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing:
In Fig. 1: ethylbenzene vaporization in heat exchanger 1 earlier, by pipeline enter in the interchanger 2 with reactor 8 in the effluent that produces carry out entering in the mixing tank 9 after the heat exchange, in mixing tank 9, mix with main water vapor.Total water vapor carries out heat exchange by pipeline input stove 3.Water vapor after the heating is imported in the intermediate heat exchanger 5, its effluent that from reactor 7, produces heating, water vapor input stove 4 after the heat exchange, be heated at this, the water vapor that comes out from stove 4 is divided into two strands, one main water vapor enters mixing tank 9 to be mixed with ethylbenzene, the quality of water vapor and ethylbenzene is 0.6～1.4: 1, when ethylbenzene and vapour mixture leave mixing tank 9, temperature is 550～650 ℃, enter in first dehydrogenation reactor 6 and react, the pressure in the reactor 6 is 0.05～0.1MPa (absolute pressure), and is better with 0.06～0.08MPa (absolute pressure).The additional steam of another strand enters in the mixing tank 10 with effluent from first dehydrogenation reactor 6 and mixes, the mass ratio of make up water steam and material ethylbenzene is 0.3～0.6: 1, temperature was 550～650 ℃ when mixture left mixing tank 10, enter in second dehydrogenation reactor 7 and react, pressure in the reactor 7 is 0.03～0.08MPa (absolute pressure), and is better with 0.04～0.06MPa (absolute pressure).From the reaction mixture inflow heat exchanger 5 that reactor 7 comes out, carry out heat exchange with water vapor, temperature after heating is 550～650 ℃, inflow reactor 8, the pressure in the reactor 8 is 0.03～0.6MPa (absolute pressure), and is better with 0.03～0.04MPa (absolute pressure).After reactor 8 effusive products reclaim heat through interchanger 1, interchanger 2 and interchanger 3, flow into product separation system (not marking the figure), after separating, get target product.
In the present invention: ethylbenzene cumulative volume air speed is 0.25～0.4 hour
-1, the total water vapor and the mass ratio of ethylbenzene are 1.2～1.8: 1.
The present invention is further elaborated below by embodiment:
Embodiment
The catalytic dehydrogenation of ethylbenzene/vapour mixture is carried out with the technical process of Fig. 1, and dehydrogenation reactor adopts the form of radial reactor.Reaction result sees Table 1.
Comparative example
The catalytic dehydrogenation of ethylbenzene/vapour mixture is carried out with the technical process of the technology that patent documentation CN1006061B is reported, reactor adopts the radial reactor form.Reaction result sees Table 1.
Table 1:
| Project | Unit | Reactor | Embodiment | Comparative example |
| The mass ratio of water vapor/ethylbenzene | Wt | First reactor | 1.1∶1 | 1.6∶1 |
| Second reactor | 1.6∶1 | 1.6∶1 | ||
| The 3rd reactor | 1.6∶1 | 1.6∶1 | ||
| Reactor inlet temperatures | ℃ | First reactor | 625 | 625 |
| Second reactor | 625 | 625 | ||
| The 3rd reactor | 625 | 625 | ||
| Mean pressure | kPaA | First reactor | 72 | 76 |
| Second reactor | 58 | 60 | ||
| The 3rd reactor | 47 | 47 | ||
| Gross space speed | hr -1 | / | 0.30 | 0.30 |
| Total conversion of ethylbenzene | ％ | / | 73 | 73 |
| Total selectivity of styrene | mol％ | / | 95.5 | 94.9 |
Claims (3)
1, improving one's methods of a kind of producing phenyl ethylene by ethyl benzene catalytic dehydrogenation, it adopts multistage composite heat-exchange reaction process, dehydrogenation comprises in three placed in-line dehydrogenation reactors at a cover at least carries out, settle a heat-exchanger rig before each reactor, reaction mass and high-temperature water vapor are through directly or indirectly entering reactor after the heat exchange, reaction mass is heated to 550～650 ℃ in each dehydrogenation reactor ingress, absolute pressure mean value in first reactor is 0.05～0.10Mpa, second reactor reaches and remains between 0.03～0.08Mpa with the absolute pressure mean value in the post-reactor, and liquid ethylbenzene cumulative volume air speed is 0.25～0.4 hour
-1Material after the dehydrogenation reaction carries out flowing into product separation system after heat is reclaimed in heat exchange through interchanger, after separating, get product, it is characterized in that, water vapor comes the reacting by heating effluent in the fs by interchanger, and be divided into two strands in subordinate phase, its main water vapor mixes with ethylbenzene in the ingress of first dehydrogenation reactor, the mass ratio of main water vapor and ethylbenzene is 0.6～1.4: 1, another burst make up water steam mixes with the first dehydrogenation reactor outlet material in the ingress of second dehydrogenation reactor, and the total water vapor of reactive system and the mass ratio of ethylbenzene are 1.2～1.8: 1.
2, as the improving one's methods of the said producing phenyl ethylene by ethyl benzene catalytic dehydrogenation of claim 1, it is characterized in that the mass ratio of wherein said main water vapor and make up water steam is 0.5～4: 1.
3, as the improving one's methods of claim 1 or 2 said producing phenyl ethylene by ethyl benzene catalytic dehydrogenation, it is characterized in that wherein said dehydrogenation reactor is radial reactor or axial-radial flow reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200410052662 CN1259294C (en) | 2004-07-09 | 2004-07-09 | Improved method for producing styrene by ethyl benzene catalyzed dehydrogenation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410052662 CN1259294C (en) | 2004-07-09 | 2004-07-09 | Improved method for producing styrene by ethyl benzene catalyzed dehydrogenation |
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| CN1259294C true CN1259294C (en) | 2006-06-14 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030522B (en) * | 2011-09-29 | 2015-02-11 | 中国石油化工股份有限公司 | Method for vaporizing raw materials for styrene preparation through ethylbenzene dehydrogenation |
| CN102675027A (en) * | 2012-05-14 | 2012-09-19 | 湖南百利工程科技股份有限公司 | Process for preparing butadiene through oxidative dehydrogenation of butene |
| CN103664497B (en) * | 2012-09-05 | 2015-07-08 | 中国石油化工股份有限公司 | Method for producing styrene employing catalytic dehydrogenation of ethylbenzene |
| CN103708989B (en) * | 2013-12-27 | 2016-06-29 | 江苏正丹化学工业股份有限公司 | A kind of dehydrogenation unit in vinyltoluene production |
| CN107540508A (en) * | 2016-06-29 | 2018-01-05 | 中石化上海工程有限公司 | The method and its equipment of a kind of producing phenyl ethylene by ethyl benzene catalytic dehydrogenation |
| WO2018118505A1 (en) * | 2016-12-20 | 2018-06-28 | Fina Technology, Inc. | Parallel reactor system for ethylbenzene dehydrogenation |
| CN108160006B (en) * | 2018-02-13 | 2023-11-14 | 镇海石化建安工程股份有限公司 | Propane dehydrogenation device and propane dehydrogenation method |
| CN113620771A (en) * | 2020-05-08 | 2021-11-09 | 中国石油化工股份有限公司 | Reaction system and reaction method for preparing divinylbenzene through dehydrogenation of diethylbenzene |
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