CN101811930B - Selective hydrogenation method for phenylacetylene in phenylacetylene-containing styrene material flow - Google Patents
Selective hydrogenation method for phenylacetylene in phenylacetylene-containing styrene material flow Download PDFInfo
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Abstract
The invention relates to a selective hydrogenation method for phenylacetylene in phenylacetylene-containing styrene material flow, which mainly solves the problem that excessive hydrogen in the selective hydrogenation process for the phenylacetylene possibly transforms the phenylacetylene and the styrene into an unexpected unsaturated product ethylbenzene so as to cause loss increment of the styrene. The invention adopts the technical scheme that raw materials and a palladium or nickel-containing catalyst in a catalyst bed layer undergo contact reaction in a gas-liquid-solid three-phase multi-section fixed bubbling bed reactor, wherein a gas distributor is arranged between the bottom of the fixed bubbling bed reactor and the catalyst bed layer; and the gas distributor comprises a gas main and branch pipes, and the branch pipe is provided with at least one row of pores or the branch pipe is provided with at least one row of open short pipes, so the problem is well solved. The method can be used in the selective hydrogenation industrial production for the phenylacetylene in the phenylacetylene-containing styrene material flow.
Description
Technical field
The present invention relates to a kind of styrene stream phenylacetylene for containing phenylacetylene and select the method for hydrogenation.
Background technology
Vinylbenzene is the important monomer of producing polystyrene, ABS resin and styrene-butadiene rubber(SBR).At present, cinnamic production method mainly contains ethylbenzene dehydrogenation method, epoxypropane-vinyl benzene (PO/SM) co-production method, pyrolysis gasoline extractive distillation absorption method and divinyl synthesis method etc. in the world.Although the ethylbenzene dehydrogenation method is to produce at present cinnamic main method both at home and abroad.But, in the last few years, along with the maximization of ethene scale, became an effective approach so that from the pyrolysis gasoline of steam cracking ethylene unit by-product, reclaim vinylbenzene.
For from pyrolysis gasoline, reclaiming cinnamic method, generally believe that at present feasible is the extractive distillation method, but, phenylacetylene is similar to cinnamic chemical structure, both are also similar to the interaction between the extractive distillation solvent, therefore can not realize the effective separation of vinylbenzene and phenylacetylene by extracting rectifying.The existence of phenylacetylene, the catalyst consumption amount in the time of not only can increasing anionic polymerization of styrene affects chain length and polymerization velocity, and can cause the polystyrene performance depreciation, such as variable color, degraded, spoiled and discharge smell etc.Therefore, for the styrene monomer stream of purifying is provided, usually adopt selective hydrogenation of phenylacetylene in the presence of corresponding styrene monomer.Select the method for hydrogenation usually fixedly to carry out in the bubbling bed reactor at gas-liquid-solid three-phase for the styrene stream phenylacetylene that contains phenylacetylene.
Gas-liquid-solid three-phase fixedly bubbling bed reactor be a kind of in catalytic reaction process the simultaneous reactor of gas phase, liquid phase and solid phase (catalyzer).In this reactor, gas phase and the liquid phase reaction logistics beds of flowing through from bottom to top respectively, this moment, liquid phase was external phase, and gas phase is disperse phase, and catalyzer is immersed in the continuous liquid phase fully, and bubble moves up with the bubbling form.
The selective hydrogenation of phenylacetylene is a series connection reaction, and the purpose product is vinylbenzene.In reaction process, if hydrogen is excessive, be undesirable saturated products ethylbenzene with phenylacetylene and styrene conversion probably, thereby cause the vinylbenzene loss amount to increase.Thereby the phenylacetylene selective hydrogenation under the vinylbenzene environment often adopts the multiple spot hydrogen feed or uses the multistage reactor.Adopt this kind form not only can effectively control hydrogen alkynes ratio, but also can effectively regulate the dissolution degree of hydrogen in oil, thus the transformation efficiency of raising phenylacetylene hydrogenation, and reduce cinnamic loss amount.Select the gas-liquid-solid three-phase multistage of hydrogenation fixedly in the bubbling bed reactor at phenylacetylene, large quantity of fluid (oil product) is when sending into reactor bottom, part gas (hydrogen) also must enter reactor after reactor bottom suitably distributes with the form of bubble, another part gas (hydrogen) is by injecting between two sections of the reactor catalysts, at this moment with regard to the gas that produced intersegmental the injection evenly mixed and mixed rear equally distributed problem of material with the first paragraph material.
The fluid well-distributing distribution of bed ingress is initial distribution, is crucial, and it directly has influence on the distribution effect in bed middle part and exit.Certainly, fixedly bubbling bed itself also is a kind of good divider, but only could only rely on the bed distribution of gas in the reactor of minor diameter.In large diameter reactor, depending merely on bed is can't realize bed equally distributed, need to the whole cross section below bed be installed by the gas distributor of sufficient amount, and then lean on bed to realize good distribution.Therefore, gas distributor plays a very important role.It has eliminated the problem of gas distribution inequality, thereby eliminates short circuit and channeling in the reactor, avoids the interior temperature difference of reactor larger, guarantees giving full play to of catalyst action, reduces cinnamic loss amount, guarantees quality and the yield of reaction product.
Intersegmental mixed requirement is fast mixed and even distribution of realizing two strands of reaction masses in limited time and space, and the material that enters next section beds is radially evenly distributed.Therefore, the installing gas sparger plays a very important role between the beds.Well behaved intersegmental gas distributor can obtain uniform assignment of traffic, can reduce sparger to the height of catalyzer, reaches good gas distribution and mixed effect.Guarantee giving full play to of catalyst action, thereby effectively suppress vinylbenzene and phenylacetylene further reacts the amount that forms ethylbenzene, guarantee quality and the yield of reaction product.But, at present relevant gas-liquid-solid three-phase multistage fixedly the article studied of bubbling bed reactor and inner member thereof seldom publish.
Patent CN200480022198.8, CN99805525.5 (WO99155648), US5156817, US6727398B2 discloses respectively the method that there is lower selective hydrogenation of phenylacetylene in a kind of styrene monomer, propose to adopt the method for multistage reactor and intersegmental hydrogen injecting oxidizing gases, but do not propose in the literary composition hydrogenated gas of introducing between the beds is distributed in advance, this will inevitably exist the hydrogenated gas of intersegmental injection to enter behind the reactor mixed inequality with the epimere material, and the material after mixed enters the problem of skewness behind the epimere beds, thereby affected the utilization ratio of epimere catalyzer, affect the hydrogenation conversion of phenylacetylene, easily cause the vinylbenzene loss amount to increase.
" catalytic reactor designs " (Beijing-scientific and technical literature press 1998) book, the gas distributor of having introduced in the fixing bubbling bed reactor only is a pipe that has some apertures thereon, gas dispersion in liquid.But the sparger of this structure formation is too simple, can not guarantee the even distribution of gas.
Summary of the invention
Technical problem to be solved by this invention is to exist hydrogen excessive in the phenylacetylene selective hydrogenation process in the prior art, is undesirable saturated products ethylbenzene with phenylacetylene and styrene conversion probably, thus the problem that causes the vinylbenzene loss amount to increase.The styrene stream phenylacetylene that provides a kind of new being used for to contain phenylacetylene is selected the method for hydrogenation.The method has the reactor inner fluid and is evenly distributed, little phenylacetylene content and the little characteristics of vinylbenzene loss amount that can obviously reduce in the styrene stream of bed radial temperature difference.
For solving the problems of the technologies described above, the present invention adopts technical scheme as follows: a kind of styrene stream phenylacetylene for containing phenylacetylene is selected the method for hydrogenation, take the styrene stream that contains phenylacetylene of vinylbenzene weight content 〉=25%, phenylacetylene weight content 〉=1000ppm and hydrogen as raw material, it is 35～70 ℃ in temperature, pressure is 0.3～1.0MPa, and liquid hourly space velocity is 1～10 hour
-1The mol ratio of hydrogen and phenylacetylene is under 1～10: 1 the condition, raw material gas-liquid-solid three-phase multistage fixedly in the bubbling bed reactor with beds in contain palladium or nickeliferous catalyzer contact reacts, make the phenylacetylene weight content≤100ppm in the styrene stream, wherein fixedly distinguish the installing gas sparger between bubbling bed reactor bottom and the beds, wherein gas distributor comprises gas main (15) and arm (16), have on the arm at least 1 row aperture (17), or on the arm with at least 1 row perforate short tube (17).
In the technique scheme, gas-liquid-solid three-phase multistage fixedly bubbling bed reactor beds is at least 2 beds; Preferred version forms mixture for comprising nitrogen in the hydrogen, and the nitrogen of mixture and the molar ratio range of hydrogen are 0～1.0.When house steward (15) is dendroid, cross distribution with each arm (16), parallel installation between each arm, spacing equates between each arm, and the arm number is 2～18, and preferable range is 4～12.When the distribution of each arm (16) distributed radially, the interval equal angular was installed between each arm, and the arm number is 2～8, and preferable range is 3～6.When the distribution of each arm is the concentric circles distribution, the equidistant installation of being separated by between each arm, the arm number is 2～8, preferable range is 2～4.When the aperture on the arm (16) or perforate short tube are 1 row, along reactor axial aperture or installation perforate short tube.When the aperture (17) on the arm (16) is 2 row, every rows of openings angle axially becomes 10～75 ° angle with reactor, preferable range is 25～60 °, and aperture (17) evenly distributes side by side on arm (16) or is interspersed, and preferred version is that aperture (17) is in the upper side by side evenly distribution of arm (16).When the perforate short tube (17) on the arm (16) was 2 row, perforate short tube (17) medullary ray axially became 10～75 ° angle with reactor, and preferable range is 25～60 °, and perforate short tube (17) is interspersed at arm (16).Aperture on the arm (16) or the aperture on the perforate short tube can be circle or ellipse, and preferred version is that aperture is circular, and the perforate total area is 0.2～2.0 times of arm sectional area, and preferable range is 0.4～1.5 times.
For gas-liquid-solid three-phase multistage fixedly bubbling bed reactor include the method that phenylacetylene in the styrene stream of phenylacetylene is selected hydrogenation, excessive in order to solve in the reaction process hydrogen in the prior art, the problem that causes the vinylbenzene loss amount to increase, although proposed to adopt the multiple spot hydrogen feed or with the method for multistage reactor, but do not consider that multiple spot advances the mode that hydrogen is introduced between hydrogen and the multistage reactor catalyst bed, can not guarantee to be uniformly distributed on the whole cross section of reactor after hydrogen enters reactor, thereby cause on the whole cross section of reactor the molar ratio of hydrogen and phenylacetylene inconsistent, part is worth excessive, and the part value is too small, must affect the performance of catalyst action, affect the transformation efficiency of phenylacetylene hydrogenation, and easily caused cinnamic loss amount to increase.New being used for that the present invention proposes contains the method for the styrene stream phenylacetylene selection hydrogenation of phenylacetylene, because at gas-liquid-solid three-phase multistage fixedly below the bubbling bed reactor beds and well behaved gas distributor has been installed respectively between the beds, guaranteed that hydrogen enters the even distribution on whole bed cross section behind the reactor, effectively regulated the homogeneity of hydrogen dissolution degree in containing the styrene stream of phenylacetylene, guaranteed the consistence of molar ratio on the whole cross section of bed of hydrogen and phenylacetylene, the same cross section of its beds uniformity coefficient maximum deviation is less than 2.0%, radial temperature difference is less than 0.5 ℃, thereby guaranteed the utilization ratio of catalyzer, be conducive to improve the transformation efficiency of phenylacetylene hydrogenation and reduce cinnamic loss amount, can make the phenylacetylene weight content minimum in the styrene stream is 0, vinylbenzene minimum loss amount is 0, has obtained preferably technique effect.
Description of drawings
Fig. 1 is fixedly bubbling bed reactor schematic diagram of gas-liquid-solid three-phase multistage.
Fig. 2 is the gas distributor schematic diagram that is the parallel distribution of dendroid.
Fig. 3 is the gas distributor schematic diagram that distributes radially.
Fig. 4 is the gas distributor schematic diagram that concentric circles distributes.
Fig. 5 is that the aperture on the arm was 1 when row, the A-A view of Fig. 2, Fig. 3, Fig. 4
Fig. 6 is that the perforate short tube on the arm was 1 when row, the A-A view of Fig. 2, Fig. 3, Fig. 4
Fig. 7 is that the aperture on the arm is 2 rows, and during column distribution, the A-A view of Fig. 2, Fig. 3, Fig. 4
Fig. 8 is that the aperture on the arm is 2 rows, when being interspersed, and the A-A of Fig. 2, Fig. 3, Fig. 4, B-B view
Fig. 9 is that the perforate short tube on the arm was 2 whens row, the A-A of Fig. 2, Fig. 3, Fig. 4, B-B view
Symbology among Fig. 1: 1 is housing, and 2 for containing the styrene stream import of phenylacetylene, and 3 is hydrogen inlet, 4 is the inlet gas sparger, and 5,10 is supporting screening plate, and 6,8,11,13 is the porcelain ball, 7,12 is beds, and 9 is intersegmental gas distributor, and 14 are the product outlet.
Symbology among Fig. 2～Fig. 9: 15 is house steward, and 16 is arm, and 17 is the aperture on the arm
Fig. 1 Raw workflow is: from the hydrogen of reactor bottom hydrogen inlet, after gas distributor through being connected with hydrogen inlet evenly distributes, after evenly mixed with the styrene stream that contains phenylacetylene of the styrene stream import that contains phenylacetylene from reactor bottom, and flow to and to enter the first paragraph beds through supporting screening plate and porcelain ball and react, reacted material enters zone between the beds through the porcelain ball, and enter the second segment beds after evenly mixed and react with hydrogen after evenly distributing from intersegmental gas distributor, reacted product is flowed out by the product outlet at last through porcelain ball and reactor upper space.
The invention will be further elaborated below by embodiment, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Press Fig. 1, Fig. 2 and Fig. 7, gas-liquid-solid three-phase multistage fixedly bubbling bed reactor diameter is 1000 millimeters, and beds is 2 layers.Catalyzer is 0.5% weight Pd/Al
2O
3Palladium-containing catalyst.Equidistantly arrange in the gas distributor of the parallel distribution of dendroid, each arm same cross section in reactor, has 2 rows' aperture on the arm, and aperture evenly distributes side by side along pipe range.100 millimeters of house steward's diameters, 4 of arms, diameter is 50 millimeters, and the aperture on the arm is circular, and diameter is 5 millimeters, and the perforate total area is 0.8 times of arm sectional area, every rows of openings angle axially becomes 30 ° angle with reactor.Hydrogen is the miscellany of hydrogen and nitrogen, and the mol ratio of nitrogen and hydrogen is 0.5.With a kind of 25 % by weight vinylbenzene that comprise, the C8 hydrocarbon fraction of 11 % by weight ethylbenzene and 1500ppm phenylacetylene joins this reactor bottom, part hydrogen also joins this reactor bottom after being distributed by the inlet gas sparger, joins the middle part of this reactor after another part hydrogen is distributed by intersegmental gas distributor.Temperature of reaction is 40 ℃, and reaction pressure is 0.3MPa, and liquid hourly space velocity is 8 hours
-1, hydrogen/phenylacetylene mol ratio remains on 1～2.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase multistage of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 2.0%, radial temperature difference is less than 0.5 ℃, and phenylacetylene content is 0 in the product that is obtained by this reactor, vinylbenzene loss amount≤0.5%.
[embodiment 2]
Press Fig. 1, Fig. 2 and Fig. 9, gas-liquid-solid three-phase multistage fixedly bubbling bed reactor diameter is 1500 millimeters, and beds is 2 layers.Catalyzer is 1.5% weight Ni/Al
2O
3Nickel-containing catalyst.Equidistantly arrange in the gas distributor of the parallel distribution of dendroid, each arm same cross section in reactor, and with 2 rows' perforate short tube, the perforate short tube evenly distributes along pipe range is staggered on the arm.100 millimeters of house steward's diameters, 8 of arms, diameter are 40 millimeters, and the aperture on the perforate short tube is circular, and diameter is 4 millimeters, and the perforate total area is 0.9 times of arm sectional area, perforate short tube medullary ray axially becomes 60 ° angle with reactor.Hydrogen is pure hydrogen.With a kind of 30 % by weight vinylbenzene that comprise, 10.5 the C8 hydrocarbon fraction of % by weight ethylbenzene and 3500ppm phenylacetylene joins this reactor bottom, part hydrogen also joins this reactor bottom after being distributed by the inlet gas sparger, joins the middle part of this reactor after another part hydrogen is distributed by intersegmental gas distributor.Temperature of reaction is 50 ℃, and reaction pressure is 0.5MPa, and liquid hourly space velocity is 3 hours
-1, hydrogen/phenylacetylene mol ratio remains on 4～5.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase multistage of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 2.5%, radial temperature difference is less than 0.8 ℃, phenylacetylene content≤10ppm in the product that is obtained by this reactor, vinylbenzene loss amount≤0.1%.
[embodiment 3]
Press Fig. 1, Fig. 2 and Fig. 5, gas-liquid-solid three-phase fixedly bubbling bed reactor diameter is 1000 millimeters, and beds is 2 layers.Catalyzer is 1.5% weight Ni/Al
2O
3Nickel-containing catalyst.Equidistantly arrange in the gas distributor of the parallel distribution of dendroid, each arm same cross section in reactor, and aperture is 1 row on the arm, and along the reactor axial aperture, aperture evenly distributes along pipe range.80 millimeters of house steward's diameters, 12 of arms, diameter are 30 millimeters, and aperture is circular, and diameter is 5 millimeters, and the perforate total area is 1.5 times of arm sectional area.Hydrogen is the miscellany of hydrogen and nitrogen, and the mol ratio of nitrogen and hydrogen is 0.3.With a kind of 35 % by weight vinylbenzene that comprise, the C8 hydrocarbon fraction of 8 % by weight ethylbenzene and 10000ppm phenylacetylene joins this reactor bottom, part hydrogen also joins this reactor bottom after being distributed by the inlet gas sparger, joins the middle part of this reactor after another part hydrogen is distributed by intersegmental gas distributor.Temperature of reaction is 55 ℃, and reaction pressure is 0.5MPa, and liquid hourly space velocity is 5 hours
-1, hydrogen/phenylacetylene mol ratio remains on 6～7.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase multistage of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 3.2%, radial temperature difference is less than 2 ℃, phenylacetylene content≤90ppm in the product that is obtained by this reactor, vinylbenzene loss amount≤3%.
[embodiment 4]
Press Fig. 1, Fig. 3 and Fig. 5, gas-liquid-solid three-phase fixedly bubbling bed reactor diameter is 1200 millimeters, and beds is 2 layers.Catalyzer is 0.5% weight Pd/Al
2O
3Palladium-containing catalyst.The gas distributor of radial distribution, each arm same cross section in the reactor equal angular of being separated by is installed, and aperture is 1 row on the arm, along the reactor axial aperture.100 millimeters of house steward's diameters, 6 of arms, diameter is 40 millimeters, and the aperture on the arm is circular, and diameter is 4 millimeters, and the perforate total area is 0.6 times of arm sectional area.Hydrogen is the miscellany of hydrogen and nitrogen, and the mol ratio of nitrogen and hydrogen is 0.8.With a kind of 30 % by weight vinylbenzene that comprise, the C8 hydrocarbon fraction of 8 % by weight ethylbenzene and 4500ppm phenylacetylene joins this reactor bottom, part hydrogen also joins this reactor bottom after being distributed by the inlet gas sparger, joins the middle part of this reactor after another part hydrogen is distributed by intersegmental gas distributor.Temperature of reaction is 60 ℃, and reaction pressure is 0.8MPa, and liquid hourly space velocity is 4 hours
-1, hydrogen/phenylacetylene mol ratio remains on 3～4.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase multistage of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 3.3%, radial temperature difference is less than 2 ℃, phenylacetylene content≤60ppm in the product that is obtained by this reactor, vinylbenzene loss amount≤2.5%.
[embodiment 5]
Press Fig. 1, Fig. 3 and Fig. 6, gas-liquid-solid three-phase fixedly bubbling bed reactor diameter is 1200 millimeters, and beds is 2 layers.Catalyzer is 1.5% weight Ni/Al
2O
3Nickel-containing catalyst.The gas distributor of radial distribution, each arm same cross section in the reactor equal angular of being separated by is installed, and the perforate short tube on the arm is 1 row, axially installs along reactor.100 millimeters of house steward's diameters, 5 of arms, diameter is 40 millimeters, and the aperture on the arm is circular, and diameter is 5 millimeters, and the perforate total area is 1.25 times of arm sectional area.Hydrogen is the miscellany of hydrogen and nitrogen, and the mol ratio of nitrogen and hydrogen is 0.2.With a kind of 35 % by weight vinylbenzene that comprise, the C8 hydrocarbon fraction of 7 % by weight ethylbenzene and 14000ppm phenylacetylene joins this reactor bottom, part hydrogen also joins this reactor bottom after being distributed by the inlet gas sparger, joins the middle part of this reactor after another part hydrogen is distributed by intersegmental gas distributor.Temperature of reaction is 55 ℃, and reaction pressure is 0.5MPa, and liquid hourly space velocity is 6 hours
-1, hydrogen/phenylacetylene mol ratio remains on 7～8.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 3.5%, radial temperature difference is less than 2.5 ℃, phenylacetylene content≤95ppm in the product that is obtained by this reactor, vinylbenzene loss amount≤3.5%.
[embodiment 6]
Press Fig. 1, Fig. 4 and Fig. 7, gas-liquid-solid three-phase fixedly bubbling bed reactor diameter is 1500 millimeters, and beds is 2 layers.Catalyzer is 1.5% weight Ni/Al
2O
3Nickel-containing catalyst.The equidistant installation of being separated by of the gas distributor that concentric circles distributes, each arm same cross section in reactor has 2 rows' apertures on the arm, aperture evenly distributes side by side along the pipe range equal angles.100 millimeters of house steward's diameters, 2 of arms, diameter is 80 millimeters, and the aperture on the arm is circular, and diameter is 5 millimeters, and the perforate total area is 0.5 times of arm sectional area, every rows of openings angle axially becomes 30 ° angle with reactor.Hydrogen is the miscellany of hydrogen and nitrogen, and the mol ratio of nitrogen and hydrogen is 0.3.With a kind of 32 % by weight vinylbenzene that comprise, the C8 hydrocarbon fraction of 10 % by weight ethylbenzene and 5000ppm phenylacetylene joins this reactor bottom, part hydrogen also joins this reactor bottom after being distributed by the inlet gas sparger, joins the middle part of this reactor after another part hydrogen is distributed by intersegmental gas distributor.Temperature of reaction is 50 ℃, and reaction pressure is 0.4MPa, and liquid hourly space velocity is 4 hours
-1, hydrogen/phenylacetylene mol ratio remains on 4～5.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 2.6%, radial temperature difference is less than 1.5 ℃, phenylacetylene content≤30ppm in the product that is obtained by this reactor, vinylbenzene loss amount≤1.5%.
[embodiment 7]
Press Fig. 1, Fig. 4 and Fig. 8, gas-liquid-solid three-phase fixedly bubbling bed reactor diameter is 1500 millimeters, and beds is 2 layers.Catalyzer is 1.5% weight Ni/Al
2O
3Nickel-containing catalyst.The gas distributor that concentric circles distributes, equidistantly arrange in each arm same cross section in reactor, on the arm with 2 rows' apertures, the equidistant installation of being separated by of each arm same cross section in reactor, aperture is interspersed along the pipe range equal angles.100 millimeters of house steward's diameters, 3 of arms, diameter is 50 millimeters, and the aperture on the arm is circular, and diameter is 5 millimeters, and the perforate total area is 1.2 times of arm sectional area, every rows of openings angle and reactor be angle at 45 ° axially.Material is identical with embodiment 6 with reaction conditions.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 2.5%, radial temperature difference is less than 1.5 ℃, phenylacetylene content≤40ppm in the product that is obtained by this reactor, vinylbenzene loss amount≤1.2%.
[embodiment 8]
Press Fig. 1, Fig. 4 and Fig. 5, gas-liquid-solid three-phase fixedly bubbling bed reactor diameter is 1200 millimeters, and beds is 2 layers.Catalyzer is 1.5% weight Ni/Al
2O
3Nickel-containing catalyst.The equidistant installation of being separated by of the gas distributor that concentric circles distributes, each arm same cross section in reactor, aperture is 1 row on the arm, along the reactor axial aperture.100 millimeters of house steward's diameters, 4 of arms, diameter is 40 millimeters, and the aperture on the arm is oval, and the perforate total area is 0.85 times of arm sectional area.Material is identical with embodiment 2 with reaction conditions.Under above structural parameter and condition, by the inventive method phenylacetylene selective hydrogenation reaction in the styrene stream that contains phenylacetylene is designed, can obtain preferably technique effect.By the fixing bubbling bed reactor of the gas-liquid-solid three-phase of the inventive method design, the same cross section of its beds uniformity coefficient maximum deviation is less than 3.2%, radial temperature difference is less than 2 ℃, phenylacetylene content≤30ppm in the product that is obtained by this reactor, vinylbenzene loss amount≤1.5%.
Claims (7)
1. a styrene stream phenylacetylene that is used for containing phenylacetylene is selected the method for hydrogenation, take the styrene stream that contains phenylacetylene of vinylbenzene weight content 〉=25%, phenylacetylene weight content 〉=1000ppm and hydrogen as raw material, it is 35～70 ℃ in temperature, pressure is 0.3～1.0MPa, and liquid hourly space velocity is 1～10 hour
-1The mol ratio of hydrogen and phenylacetylene is under 1～10: 1 the condition, raw material gas-liquid-solid three-phase multistage fixedly in the bubbling bed reactor with beds in contain palladium or nickeliferous catalyzer contact reacts, make the phenylacetylene weight content≤100ppm in the styrene stream, wherein fixedly distinguish the installing gas sparger between bubbling bed reactor bottom and the beds, wherein gas distributor comprises gas main and arm, have on the arm at least 1 row aperture, or on the arm with at least 1 row the perforate short tube;
Be distributed as house steward and each arm of each arm are cross and distribute, parallel installation between each arm, and spacing equates between each arm, is dendroid, the arm number is 4～12; Perhaps the interval equal angular that is distributed as between each arm of each arm is installed, and distributes radially, and the arm number is 3～6.
2. the styrene stream phenylacetylene for containing phenylacetylene according to claim 1 is selected the method for hydrogenation, it is characterized in that beds is at least 2 beds.
3. the styrene stream phenylacetylene for containing phenylacetylene according to claim 1 is selected the method for hydrogenation, it is characterized in that comprising in the described hydrogen nitrogen and forms mixture, and the mol ratio of the nitrogen/hydrogen of mixture is 0～1.0: 1.
4. the method for selecting hydrogenation for the styrene stream phenylacetylene that contains phenylacetylene according to claim 1 is when is characterized in that aperture on each arm or perforate short tube are 1 row, along the reactor axial aperture or the perforate short tube is installed.
5. the styrene stream phenylacetylene for containing phenylacetylene according to claim 1 is selected the method for hydrogenation, when it is characterized in that aperture on each arm is 2 row, every rows of openings angle axially becomes 25～60 ° angle with reactor, and aperture evenly distributes side by side on arm or is interspersed.
6. the styrene stream phenylacetylene for containing phenylacetylene according to claim 1 is selected the method for hydrogenation, when it is characterized in that perforate short tube on each arm is 2 row, perforate short tube medullary ray axially becomes 25～60 ° angle with reactor, and the perforate short tube is interspersed at arm.
7. the styrene stream phenylacetylene for containing phenylacetylene according to claim 1 is selected the method for hydrogenation, it is characterized in that aperture or the aperture on the perforate short tube on each arm is circle, and the perforate total area is 0.4～1.5 times of arm sectional area.
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| US9849434B2 (en) * | 2010-09-22 | 2017-12-26 | Grupo Petrotemex, S.A. De C.V. | Methods and apparatus for enhanced gas distribution |
| CN101961623A (en) * | 2010-09-26 | 2011-02-02 | 铜陵钱陵化工设备制造有限公司 | Double-layer double-safety autoclave with discharge pipe orifices |
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| CN2604434Y (en) * | 2003-01-30 | 2004-02-25 | 西南化工研究设计院 | Bubble tower converter for technology of methyl alcohol low pressure liquid phase carbonyl synthesizing acetic acid |
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