CN1962029A - Method for separating dehydrogenated tail gas - Google Patents
Method for separating dehydrogenated tail gas Download PDFInfo
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- CN1962029A CN1962029A CN 200510110273 CN200510110273A CN1962029A CN 1962029 A CN1962029 A CN 1962029A CN 200510110273 CN200510110273 CN 200510110273 CN 200510110273 A CN200510110273 A CN 200510110273A CN 1962029 A CN1962029 A CN 1962029A
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- tail gas
- separating
- ethylbenzene
- dehydrogenated tail
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for separating dehydrogenation tail gas, wherein the invention uses dehydrogenation product to pass the film separator formed by tube and frame; the frame process uses inertia gas to blow and vacuum the hydrogen separated from the film separator. The invention can be used in phenylethene industry.
Description
Technical field
The present invention relates to a kind of method that is used for separating dehydrogenated tail gas.
Background technology
China's styrene is mainly used in produces polystyrene, ABS, AS, unsaturated polyester resin, butadiene-styrene rubber, styrene-butadiene latex and styrene series thermoplastic elastomer etc., and China's aggregate consumption was about 3,200,000 tons in 2003, estimates will reach 3,960,000 tons in 2005.Along with China's building materials, household electrical appliances and rapid development of automobile industry, the consumption figure of p-poly-phenyl ethene, ABS and SBR, SBS etc. will further increase, and tackling cinnamic demand mutually also will constantly increase.Estimate that China's styrene in 2005 still needs a large amount of imports.
At present, production of styrene method in the world's mainly contains ethylbenzene catalytic dehydrogenation method, oxidative dehydrogenation of ethylbenzene method, styrene/propylene oxide co-production method.China's styrene mainly adopts the ethylbenzene dehydrogenation method to produce.Because be subjected to the restriction of thermodynamical equilibrium, conversion of ethylbenzene only is about 65% on the commercial plant, still has bigger distance from equilibrium conversion.How further improving conversion of ethylbenzene or increase the ethylbenzene treating capacity, come by styrene output, is the key point of styrene manufacturing technology.
Membrane catalytic reaction realization response and isolation integral, not only can simplify flow process, the economy system investment, reduce advantages such as operation energy consumption, also those are subjected to thermodynamics equilibrium limit and can not improve the chemical reaction of conversion ratio,, product is separated constantly, selectively from reaction system by reaction and the coupling that separates, the restriction of disequilibrating increases substantially conversion ratio.Also can increase simultaneously the inventory of raw material, to improve the output of purpose product.
In order to improve cinnamic conversion ratio and output, the expert has carried out a large amount of research both at home and abroad, main method has: the performance of 1) improving catalyst, as United States Patent (USP) 5668075,5689023, world patent WO96/18594, European patent 0093518 grade has been studied in the catalyst preparation process raw material to the performance impact of catalyst.2) utilize hydrogen in the selective oxidation method minimizing system, as U.S. Pat 5994606, US5043500, European patent EP 336622B189, EP826418A197 etc. have introduced the method that Smart technology improves general conversion ratio.The leeway that method 1 improves is more and more littler, especially improves more difficult under hot conditions.Method 2 can partly improve the conversion ratio of reaction, but can only burn 60% hydrogen, and high to security requirement, thereby investment is bigger.And owing to use noble metal as oxidation catalyst, the catalyst cost is higher.Owing to inevitably aromatic hydrocarbons is produced certain consumption in the oxidizing process, the device material consumption is higher and selectivity of styrene is slightly poor again.
Summary of the invention
Technical problem to be solved by this invention is the Pt/Al that uses that exists in the conventional art
2O
3The selective oxidation hydrogen partial, oxidation of hydrogen is incomplete, and conversion ratio improves little and cost of investment is high, safety requirements is high, selectivity descends, the material consumption problem of higher, and a kind of new method that is used for separating dehydrogenated tail gas is provided.This method has good separating effect, can improve conversion ratio, reduced investment, the advantage that operating cost is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for separating dehydrogenated tail gas, the tube side of the membrane separator that dehydrogenated product stream is formed via tube side and shell side, shell side are used and dehydrogenation product are the method that inert gasses purges or vacuumize the membrane separator separated hydrogen is taken away.
In the such scheme, be the inert gasses preferred version and be selected from nitrogen, helium or water vapour; Mol ratio preferable range between inert gas purge amount and the ethylbenzene feed amount is 5～30: 1; System pressure preferable range when vacuumizing is-30～-70KPa.
The method that is used for separating dehydrogenated tail gas provided by the invention is used dehydrogenation product to be the method that inert gasses purges, vacuumizes the membrane separator separated hydrogen is taken away; And membrane separator is connected with traditional fixed bed reactors, forming the compound mode of reaction and isolation integral, conversion of ethylbenzene can effectively improve, and selectivity also increases, thereby helps reducing the energy consumption of industrial installation.
The preparation method of film pipe of the present invention is as follows: with Al
2O
3H
2O is a raw material, separates, refluxes, agingly makes transparent granule acidic sol through acidolysis, glue, adds binding agent in this colloidal sol, make coating liquid, coating liquid evenly is applied on the micropore ceramics,, makes surface inorganic ceramic membrane pipe uniformly after drying 450-650 ℃ of following roasting.The inorganic ceramic membrane pipe is fixed in the stainless steel separator, the component film separator, head and the tail link to each other with the isotherm formula fixed bed reactors, form the quick-reading flow sheets of isothermal reactor 1-membrane separator 2-isothermal reactor 3.The flow through film pipe of membrane separator of the effluent of isothermal reactor 1 leads to inert gas in the outer infiltration chamber of film pipe and purges or vacuumize.
Dehydrogenation reaction effect before and after membrane separator adopts is verified that by ethylbenzene dehydrogenation reaction its process is summarized as follows:
Deionized water and ethylbenzene are imported preheating mixer through measuring pump respectively, enter reactor 1 after the preheating, reactor 1 adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters, particle diameter is 3 millimeters a catalyst.Reactor 1 outlet is connected with membrane separator 2 or reactor 3 by two-way valve, and the form of reactor 3 is with reactor 1.The dehydrogenation product that reactor 3 flows out is analyzed its composition with gas chromatograph behind water condensation.
At inert gas is water vapour, and the mol ratio between inert gas purge amount and the ethylbenzene feed amount is 10: 1, and pressure is under the normal pressure, and conversion of ethylbenzene is 79.6%, and selectivity of styrene reaches 95.6%, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Be respectively 620 ℃ at first, second reactor inlet temperature, air speed 2.0 hours
-1, water/ethylbenzene weight ratio is 2.0, pressure is under the condition of normal pressure, and ethylbenzene and water vapour are mixed in proportion the combined reactor that the back feeding contains membrane separator.Logistics is to go out on advancing under first reactor in proper order, goes out under membrane separator is enterprising, goes out on advancing under second reactor.In the infiltration chamber of membrane separator, feed an amount of N
2, regulate nitrogen/ethylbenzene mol ratio.The reaction chamber product taken a sample after condensation carry out chromatography, obtain conversion of ethylbenzene, selectivity of styrene.Whole separator adopts outer heating to be incubated, and temperature is controlled at 300 ℃.Reaction condition and the results are shown in Table 1.
[embodiment 2～3]
Reaction condition is with embodiment 1, but replaces nitrogen with helium and water vapour respectively.Actual conditions sees Table 1.
[comparative example 1]
Adopt traditional dehydriding, promptly without membrane reactor, all the other are with embodiment 1.Actual conditions sees Table 1.
[comparative example 2]
Inert gas is a water vapour, but changes the mol ratio of inert gas and ethylbenzene into 20: 1, and all the other are with embodiment 1.Actual conditions sees Table 1.
[comparative example 3～4]
To lead to inert gas purge and change into and vacuumizing, all the other are with embodiment 1.The vacuum of comparative example 3,4 is controlled at respectively-40KPa and-60KPa.Actual conditions sees Table 1.
Table 1 reaction condition and result
| Whether lead to filmed passing tube | The inert gas kind | Inert gas/ethylbenzene mol ratio | Conversion of ethylbenzene % | Selectivity of styrene % | |
| Embodiment 1 | By | Nitrogen | 10∶1 | 78.4 | 95.5 |
| Embodiment 2 | By | Water vapour | 10∶1 | 79.6 | 95.6 |
| Embodiment 3 | By | Helium | 10∶1 | 78.5 | 95.4 |
| Comparative example 1 | Do not pass through | - | - | 70.2 | 93.8 |
| Comparative example 2 | By | Water vapour | 20∶1 | 78.1 | 95.5 |
| Comparative example 3 | By | Vacuumize system pressure-40KPa | - | 70.9 | 94.0 |
| Comparative example 4 | By | Vacuumize system pressure-60KPa | - | 71.2 | 94.2 |
Claims (4)
- The tube side of the membrane separator that 1, a kind of method that is used for separating dehydrogenated tail gas, dehydrogenated product stream are formed via tube side and shell side, shell side are used and dehydrogenation product are the method that inert gasses purges or vacuumize the membrane separator separated hydrogen is taken away.
- 2, according to the described method that is used for separating dehydrogenated tail gas of claim 1, it is characterized in that being inert gasses and be selected from nitrogen, helium or water vapour.
- 3,, it is characterized in that the mol ratio between inert gas purge amount and the ethylbenzene feed amount is 5～30: 1 according to the described method that is used for separating dehydrogenated tail gas of claim 1.
- 4, according to the described method that is used for separating dehydrogenated tail gas of claim 1, the system pressure when it is characterized in that vacuumizing is-30～-70KPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510110273 CN1962029A (en) | 2005-11-11 | 2005-11-11 | Method for separating dehydrogenated tail gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510110273 CN1962029A (en) | 2005-11-11 | 2005-11-11 | Method for separating dehydrogenated tail gas |
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|---|---|
| CN1962029A true CN1962029A (en) | 2007-05-16 |
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| CN 200510110273 Pending CN1962029A (en) | 2005-11-11 | 2005-11-11 | Method for separating dehydrogenated tail gas |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908868A (en) * | 2014-04-15 | 2014-07-09 | 大连理工大学 | Separation method for removing styrene from ethylbenzene-dehydrogenation tail gas and recovering hydrogen |
| CN104548862A (en) * | 2015-02-05 | 2015-04-29 | 中石化上海工程有限公司 | Energy-saving method for styrene plant dehydrogenation tail gas treatment system |
| CN109574779A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of 2- alkyl anthracene |
-
2005
- 2005-11-11 CN CN 200510110273 patent/CN1962029A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908868A (en) * | 2014-04-15 | 2014-07-09 | 大连理工大学 | Separation method for removing styrene from ethylbenzene-dehydrogenation tail gas and recovering hydrogen |
| CN103908868B (en) * | 2014-04-15 | 2016-03-02 | 大连理工大学 | Remove the method for styrene and recover hydrogen in ethylbenzene dehydrogenation tail gas |
| CN104548862A (en) * | 2015-02-05 | 2015-04-29 | 中石化上海工程有限公司 | Energy-saving method for styrene plant dehydrogenation tail gas treatment system |
| CN109574779A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of 2- alkyl anthracene |
| CN109574779B (en) * | 2017-09-28 | 2021-03-12 | 中国石油化工股份有限公司 | Method for producing 2-alkyl anthracene |
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