CN102649681B - Method for removing phenylacetylene through highly selective catalytic hydrogenation - Google Patents
Method for removing phenylacetylene through highly selective catalytic hydrogenation Download PDFInfo
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Abstract
The invention relates to a method for removing phenylacetylene through highly selective catalytic hydrogenation, and mainly solves the technical problems of low hydrogenation rate of phenylacetylene and high loss rate of styrene in the prior art. Through the adoption of the technical scheme that hydrocarbon fractions containing phenylacetylene are taken as raw materials, and under the conditions that the reaction temperature is 15 to 100 DEG C, the weight space velocity is 0.01 to 100 hours <-1>, the mol ratio of hydrogen to phenylacetylene is (1 to 30) : 1, and the reaction pressure is -0.08 to 5.0 MPa, the raw materials are in contact with a metal oxide catalyst in a rotary packed bed reactor, and phenylacetylene in a reaction effluent is hydrogenated to form styrene. Therefore, the invention solves the problems well, and can be used in the industrial production of removing phenylacetylene in the presence of styrene.
Description
Technical field
The present invention relates to a kind of method of phenylacetylene highly selective catalyzed reaction hydrogenation, particularly about taking containing the C8 hydrocarbon fraction of phenylacetylene as raw material, the method for removing phenylacetylene reaction.
Background technology
Vinylbenzene (ST) is the important monomer of producing polystyrene (PS), ABS resin and styrene-butadiene rubber(SBR) etc.Its production method, taking ethylbenzene dehydrogenation method as main, in recent years, along with the development of ethylene industry and the maximization of scale, makes extracting and reclaiming vinylbenzene technology from pyrolysis gasoline become one of volume increase vinylbenzene technology receiving much concern.
Pyrolysis gasoline is the by-product of ethylene industry, output is about 60%～70% of ethene production capacity, rich in styrene and xylol in C8 fraction wherein, a set of 1000kt/a ethylene unit, can obtain the vinylbenzene of 24～42kt/a, recyclable xylol simultaneously, makes cracking C8 fraction be upgraded to chemistry from fuel value and is worth, and from pyrolysis gasoline, the cinnamic production cost of extracting and reclaiming is about 1/2 of dehydrogenation of ethylbenzene to styrene.
From pyrolysis gasoline, reclaim cinnamic method, generally believe that at present feasible is extractive distillation method, but, phenylacetylene (PA) is similar to cinnamic chemical structure, interaction between both and extractive distillation solvent is also similar, therefore can not realize vinylbenzene by extracting rectifying and separate with the effective of PA.And the existence of PA, the catalyst consumption amount not only can increase anionic polymerization of styrene time, affects chain length and polymerization velocity, and can cause polystyrene performance depreciation, as variable color, degraded, spoiled and discharge smell etc.Therefore, exploitation highly selective Selective Hydrogenation Catalyst Phenylacetylene and technique become core and the key of pyrolysis gasoline extracting and reclaiming vinylbenzene technology.In addition, what need special concern is, under existing, vinylbenzene carries out in phenylacetylene hydrogenation process, how to reduce to greatest extent cinnamic loss and be in pyrolysis gasoline extracting and reclaiming vinylbenzene one of the key technical index of competitive power that whether possesses skills, cinnamic loss is lower, its Technical Economy is better, and technological competitiveness is stronger.
Patent CN1852877A, discloses a kind of method of phenylacetylene contaminant of reducing under styrene monomer exists.The styrene monomer stream that comprises a small amount of phenylacetylene is supplied with to hydrogenation reactor, also supply with hydrogeneous hydrogenated gas.Styrene monomer stream is contacted with the beds that comprises catalyzer with hydrogen, and described catalyzer is included in the copper compound of the reduction on θ alumina supporter.Hydrogenation reactor is at least 60 DEG C of temperature and at least under 30psig pressure, operate hydrogenation of phenylacetylene generation vinylbenzene.Hydrogenated gas comprises the mixture of nitrogen and hydrogen, and this technology temperature of reaction is higher, and phenylacetylene hydrogenation rate low (approximately 70%) exists catalyst life shorter simultaneously, and vinylbenzene exists rate of loss high (approximately 3% left and right).
Patent CN10878902A, a kind of method and apparatus that adopts hydride process to carry out the styrene monomer in purified styrene stream is disclosed, it is by adopting hydrogen to add thinner to dilute hydrogen as nitrogen, discharge gas with ethylbenzene dehydrogenation hydrogen is provided, making phenylacetylene contaminant hydrogenation by the reactor of multistage catalytic bed is vinylbenzene, but in this patent catalyzer, only speak of on the one hand lower concentration if the selectivity of 300ppm phenylacetylene content is except alkynes method, to phenylacetylene hydrogenation rate low (95% left and right), there is the problem that rate of loss is high in vinylbenzene simultaneously.
The EP0023745A3 patent that Imperial Chemical Industries of Britain (ICI) propose, mentions rotating bed and can be used for the processes such as absorption, parsing, distillation, but does not disclose the utilisation technology of industrially scalable.CN1064338A discloses the method for utilizing rotating bed to carry out oil-field flooding deoxidation; CN1116146A discloses a kind of method of preparing ultrafine particle under super gravity field.
Super gravity field technology is the new technology that early eighties just occurs, its internal mechanism is also continuing exploration, research for application and development is still constantly being carried out, new Application Areas is also in continuous developing, it is not also applied to the report of the production of hydrogenate phenylacetylene reaction under vinylbenzene for now as efficient mass transfer and conversion unit about high-efficiency rotating bed of packings.
Summary of the invention
Technical problem to be solved by this invention is in conventional art, in phenylacetylene hydrogenation process, to exist phenylacetylene hydrogenation rate low, the technical problem that vinylbenzene rate of loss is high.A kind of method of new phenylacetylene highly selective catalyzed reaction hydrogenation is provided.It is high that the method has phenylacetylene hydrogenation rate, the advantage that vinylbenzene rate of loss 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 of phenylacetylene highly selective catalyzed reaction hydrogenation, taking the hydrocarbon fraction containing phenylacetylene as raw material, 15～100 DEG C of temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/phenylacetylene mol ratio is 1～30: 1, reaction pressure is under the condition of-0.08～5.0MPa, raw material contacts with the metal oxide catalyst in rotary packed bed reactor, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, wherein rotary packed bed reactor comprises reactor shell (8), the first gas inlet (1), rotary-catalytic agent bed (2), fluid inlet (4) and liquid distributor (9), it is characterized in that upper the second gas inlet (10) in addition of rotary packed bed reactor fluid inlet (4), rotary-catalytic agent bed (2) is fixed on motor shaft (11), the bottom of reactor shell (8) is provided with liquid outlet (7).
In the technical program, in reactor fluid inlet pipeline, liquid distributor is set, the rotating speed of reactor is 300～2000 revs/min.
In the technical program, reaction conditions is preferably: temperature of reaction is 25～80 DEG C, and weight space velocity is 1～60 hour
-1, hydrogen/phenylacetylene mol ratio is 1～20: 1, reaction pressure is 0～2.0MPa; Metal oxide catalyst active ingredient is preferably selected from metallic nickel, and carrier is preferably selected from aluminum oxide.
As everyone knows, on the earth, all substances are all because gravity is by earth attraction, super gravity field is the environment more much bigger than earth gravity intensity of field, and material suffered power under super gravity field is called hypergravity, utilizes hypergravity the principles of science and the practical technique that produces is called high-gravity technology.
High-gravity technology is the new technology of strengthening polyphasic flow transmission and reaction process, since eighties of last century is come out, at home and abroad paid attention to widely, due to it broad applicability and have that the volume that legacy equipment do not have is little, lightweight, energy consumption is low, easy running, easy-maintaining, safety, the advantage such as can conform reliably, flexibly and more, make high-gravity technology have wide commercial applications prospect in the industrial circles such as environmental protection and material biochemical industry.But high-gravity technology, also mainly in the application and development stage, embodies a concentrated reflection of the gas-solid fluidization technology of hypergravity and two aspects of hypergravity gas-liquid mass transferring technology at present.
Under the Elevated Gravity of large hundreds of times to thousand times than earth gravity field, huge shearing force is torn into liquid liquid film, brin, the drop of micron to nano grade, produce huge, the quick phase interface upgrading, greatly increase gas-to-liquid contact specific surface area, make 1～3 order of magnitude of raising in interphase mass transfer speed ratio tradition tower, microcosmic mixes and mass transfer process is greatly strengthened.Make the production efficiency of unit equipment volume obtain the raising of 1～2 order of magnitude.
The rotary packed bed reactor adopting in the present invention, relatively simple for structure owing to having adopted, the rotary-catalytic agent bed that volume is little replaces huge equipment in traditional technology.Make whole system compact to design, easy and simple to handle, operation and maintenance cost is low, and floor space is little, and turndown ratio is large.Can significantly reduce processing cost.Simultaneously in rotary packed bed reactor two gas inletes the effective distribution that can optimize to greatest extent gas-liquid mass transfer and hydrogen is set, further avoid local distribution inequality, and then significantly improve phenylacetylene hydrogenation rate, reduce vinylbenzene rate of loss.
Brief description of the drawings
Fig. 1 is the schema of the rotary packed bed reactor that adopts of the present invention
1-first gas inlet 2-rotary-catalytic agent bed 3-pneumatic outlet 4-fluid inlet 5-fluid inlet pipeline 6-liquid outlet pipeline 7-liquid outlet 8-reactor shell 9-liquid distributor 10-the second gas inlet 11-motor shaft in figure.
Rotary packed bed reactor the present invention being adopted below in conjunction with accompanying drawing elaborates.
The rotary packed bed reactor that the present invention adopts, adopt reactor shell 8, the first gas inlet 1, rotary-catalytic agent bed 2, fluid inlet 4 and liquid distributor 9, wherein on reactor fluid inlet 4, also has the second gas inlet 10, rotary-catalytic agent bed 2 is fixed on motor shaft 11, and the bottom of reactor shell 8 is provided with liquid outlet 7.In reactor fluid inlet 4 pipelines, liquid distributor 13 is set, is mainly used in being uniformly distributed of liquid.
Two gas inletes of this reactor enter respectively the hydrogen of different amounts, and it is raw material that fluid inlet 4 enters containing the hydrocarbon fraction of phenylacetylene.Rotary-catalytic agent bed preferably adopts frequency control motor.
When work, be that raw material is introduced in reactor rotary-catalytic agent bed 2 from the first gas inlet 1, the second gas inlet 10 and fluid inlet 4 respectively by first strand of hydrogen, second strand of hydrogen and the hydrocarbon fraction containing phenylacetylene, wherein the introducing of first strand of hydrogen is that the pressure reduction being formed by system is realized.The hydrocarbon fraction containing phenylacetylene of introducing by fluid inlet pipeline 5 converges the fluid inlet 4 of rear introducing reactor and enters liquid distributor 9 and rotary-catalytic agent bed 2 with second strand of hydrogen introducing by the second gas inlet 10, gas, liquid fully contact in rotary-catalytic agent bed, and the way of contact adopts adverse current, cross-flow all can.Hydrogen in gas is with the hydrocarbon fraction containing phenylacetylene after reacting, and the hydrogen of surplus is discharged by venting port 3, and reacted liquid is discharged by fluid pipeline 6 by the liquid outlet 7 of reactor.
In above-mentioned reactor, the rotating speed of rotary-catalytic agent bed is 100～10000rpm, wherein the selected of the rotating speed of rotary-catalytic agent bed mainly determined by the inlet amount of liquid, if the motor of rotary-catalytic agent bed is frequency control motor, can in above-mentioned rotating speed, carry out continuous setup according to the introduction volume of the inlet amount of liquid and hydrogen.
Adopt technical scheme of the present invention, taking the hydrocarbon fraction containing phenylacetylene as raw material, 15～100 DEG C of temperature of reaction, weight space velocity is 0.01～100 hour
-1hydrogen/phenylacetylene mol ratio is 1～30: 1, reaction pressure is under the condition of-0.08～5.0MPa, raw material contacts with the metal oxide catalyst in rotary packed bed reactor, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, and its reaction result is: the hydrogenation rate of phenylacetylene can reach 100%, and vinylbenzene can reach free of losses, even part phenylacetylene adds as vinylbenzene and occurs that vinylbenzene increases (or vinylbenzene loss for negative value), has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Adopt the device shown in accompanying drawing 1, in molar percentage, containing 40% vinylbenzene, 10% ethylbenzene, carbon eight cuts of 0.1% phenylacetylene are raw material, taking Ni aluminum oxide as catalyzer (content of nickel is 20% by weight percentage), and be seated in rotary-catalytic agent bed, the mol ratio of first strand of hydrogen and second strand of hydrogen is 5: 1, and in total hydrogen and raw material, the mol ratio of phenylacetylene is 1.5: 1, and the inlet amount of first strand of hydrogen is 10 mols/hr.Then first strand of hydrogen, second strand of hydrogen and the hydrocarbon fraction raw material containing phenylacetylene are introduced in high efficiency reactor rotary-catalytic agent bed 2 from the first gas inlet 1, the second gas inlet 10 and fluid inlet 4 respectively, rotary-catalytic agent bed rotating speed is adjusted to 1000rpm, and wherein the introducing of first strand of hydrogen is that the pressure reduction being formed by system is realized.The hydrocarbon fraction containing phenylacetylene of introducing by fluid inlet pipeline 5 converges the fluid inlet 4 of rear introducing high efficiency reactor and enters liquid distributor 9 and rotary-catalytic agent bed 2 with second strand of hydrogen introducing by the second gas inlet 10, gas, liquid carry out abundant contact reacts in rotary-catalytic agent bed, and the way of contact adopts adverse current.Hydrogen in gas is with the hydrocarbon fraction containing phenylacetylene after reacting, and the hydrogen of surplus is discharged by venting port 3, and reacted liquid is discharged by fluid pipeline 6 by the liquid outlet 7 of high efficiency reactor.Temperature of reaction is 40 DEG C, and pressure is 0.1MPa, and its result is, cinnamic rate of loss is 0.01%, and the transformation efficiency of phenylacetylene is 100%.
[embodiment 2]
Adopt the device shown in accompanying drawing 1, in molar percentage, containing 40% vinylbenzene, 10% ethylbenzene, carbon eight cuts of 0.1% phenylacetylene are raw material, taking Ni aluminum oxide as catalyzer (content of nickel is 20% by weight percentage), and be seated in rotary-catalytic agent bed, the mol ratio of first strand of hydrogen and second strand of hydrogen is 5: 1, and in total hydrogen and raw material, the mol ratio of phenylacetylene is 1.5: 1, and the inlet amount of first strand of hydrogen is 10 mols/hr.Then first strand of hydrogen, second strand of hydrogen and the hydrocarbon fraction raw material containing phenylacetylene are introduced in high efficiency reactor rotary-catalytic agent bed 2 from the first gas inlet 1, the second gas inlet 10 and fluid inlet 4 respectively, rotary-catalytic agent bed rotating speed is adjusted to 500rpm, and wherein the introducing of first strand of hydrogen is that the pressure reduction being formed by system is realized.The hydrocarbon fraction containing phenylacetylene of introducing by fluid inlet pipeline 5 converges the fluid inlet 4 of rear introducing high efficiency reactor and enters liquid distributor 9 and rotary-catalytic agent bed 2 with second strand of hydrogen introducing by the second gas inlet 10, gas, liquid carry out abundant contact reacts in rotary-catalytic agent bed, and the way of contact adopts adverse current.Hydrogen in gas is with the hydrocarbon fraction containing phenylacetylene after reacting, and the hydrogen of surplus is discharged by venting port 3, and reacted liquid is discharged by fluid pipeline 6 by the liquid outlet 7 of high efficiency reactor.Temperature of reaction is 40 DEG C, and pressure is 0.1MPa, and its result is, cinnamic rate of loss is-0.01%, and the transformation efficiency of phenylacetylene is 100%.
[embodiment 3]
Adopt the device shown in accompanying drawing 1, in molar percentage, containing 40% vinylbenzene, 10% ethylbenzene, carbon eight cuts of 0.1% phenylacetylene are raw material, taking Ni aluminum oxide as catalyzer (content of nickel is 20% by weight percentage), and be seated in rotary-catalytic agent bed, the mol ratio of first strand of hydrogen and second strand of hydrogen is 5: 1, and in total hydrogen and raw material, the mol ratio of phenylacetylene is 1.5: 1, and the inlet amount of first strand of hydrogen is 10 mols/hr.Then first strand of hydrogen, second strand of hydrogen and the hydrocarbon fraction raw material containing phenylacetylene are introduced in high efficiency reactor rotary-catalytic agent bed 2 from the first gas inlet 1, the second gas inlet 10 and fluid inlet 4 respectively, rotary-catalytic agent bed rotating speed is adjusted to 2000rpm, and wherein the introducing of first strand of hydrogen is that the pressure reduction being formed by system is realized.The hydrocarbon fraction containing phenylacetylene of introducing by fluid inlet pipeline 5 converges the fluid inlet 4 of rear introducing high efficiency reactor and enters liquid distributor 9 and rotary-catalytic agent bed 2 with second strand of hydrogen introducing by the second gas inlet 10, gas, liquid carry out abundant contact reacts in rotary-catalytic agent bed, and the way of contact adopts adverse current.Hydrogen in gas is with the hydrocarbon fraction containing phenylacetylene after reacting, and the hydrogen of surplus is discharged by venting port 3, and reacted liquid is discharged by fluid pipeline 6 by the liquid outlet 7 of high efficiency reactor.Temperature of reaction is 40 DEG C, and pressure is 0.1MPa, and its result is, cinnamic rate of loss is-0.02%, and the transformation efficiency of phenylacetylene is 100%.
[embodiment 4]
According to the condition of embodiment 1 and device, just rotary-catalytic agent bed rotating speed is adjusted to 5000rpm, and gas, liquid carry out abundant contact reacts in rotary-catalytic agent bed, and the way of contact adopts and flows.Its result is, cinnamic rate of loss is-0.02%, and the transformation efficiency of phenylacetylene is 99.9%.
[embodiment 5]
According to the condition of embodiment 1 and device, just rotary-catalytic agent bed rotating speed is adjusted to 3000rpm, and gas, liquid carry out abundant contact reacts in rotary-catalytic agent bed, and the way of contact adopts and flows.Its result is, cinnamic rate of loss is 0, and the transformation efficiency of phenylacetylene is 100%.
[comparative example 1]
According to the reaction conditions of embodiment 1, gas-liquid total feed, just reactor adopts the fixed-bed reactor in conventional gravity field, and the catalyzer in gas, liquid and fixed-bed reactor carries out abundant contact reacts.Its result is, cinnamic rate of loss is 1%, and the transformation efficiency of phenylacetylene is 95%.
Claims (2)
1. a method for phenylacetylene highly selective catalyzed reaction hydrogenation, taking the hydrocarbon fraction containing phenylacetylene as raw material, 15～100 DEG C of temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/phenylacetylene mol ratio is 1～30:1, reaction pressure is under the condition of-0.08～5.0MPa, raw material contacts with the metal oxide catalyst in rotary packed bed reactor, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, wherein rotary packed bed reactor comprises reactor shell (8), the first gas inlet (1), rotary-catalytic agent bed (2), fluid inlet (4) and liquid distributor (9), it is characterized in that upper the second gas inlet (10) in addition of rotary packed bed reactor fluid inlet (4), rotary-catalytic agent bed (2) is fixed on motor shaft (11), the bottom of reactor shell (8) is provided with liquid outlet (7), in reactor fluid inlet (4) pipeline, liquid distributor (9) is set, the rotating speed of reactor is 300～2000 revs/min.
2. a kind of method of phenylacetylene highly selective catalyzed reaction hydrogenation according to claim 1, is characterized in that temperature of reaction is 25～80 DEG C, and weight space velocity is 1～60 hour
-1, hydrogen/phenylacetylene mol ratio is 1～20:1, reaction pressure is 0～2.0MPa; Metal oxide catalyst active ingredient is selected from metallic nickel, and carrier is selected from aluminum oxide.
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| CN112705117B (en) * | 2019-10-25 | 2022-07-12 | 中国石油化工股份有限公司 | Liquid phase hydrogenation reactor and hydrogenation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| CN101475438A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Selective hydrogenation method for phenylacetylene in the presence of phenylethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| CN101475438A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Selective hydrogenation method for phenylacetylene in the presence of phenylethylene |
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