CN102641696A - Multilayered fluidized bed for alkylation reaction of phenolic compounds and application of multilayered fluidized bed - Google Patents
Multilayered fluidized bed for alkylation reaction of phenolic compounds and application of multilayered fluidized bed Download PDFInfo
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- CN102641696A CN102641696A CN2012101221873A CN201210122187A CN102641696A CN 102641696 A CN102641696 A CN 102641696A CN 2012101221873 A CN2012101221873 A CN 2012101221873A CN 201210122187 A CN201210122187 A CN 201210122187A CN 102641696 A CN102641696 A CN 102641696A
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Abstract
Disclosed is a multilayered fluidized bed for alkylation reaction of phenolic compounds. More than two layers of composite baffles are placed in a fluidized bed cylinder so as to form the multilayered fluidized bed, the composite baffles are placed horizontally, peripheral edges of the composite baffles contact with the inner wall of the fluidized bed cylinder, the upper side of each composite baffle is a relatively independent compartment, each compartment is independently filled with catalyst particles, and accordingly a primary fluidized bed is formed. The composite baffles consist of horizontal tube banks at the bottom layer, a plurality of short pipes are welded to form the horizontal tube banks, the insides of the short pipes are communicated, one ends of the short pipes are communicated with water inlet vertical pipes, the other ends of the short pipes are communicated with insides of water outlet vertical pipes and are welded firmly, a layer of rough screens is arranged on the horizontal tube tanks, the outer diameters of the rough screens are identical to the inner diameter of the fluidized bed cylinder, a layer of fine screens are arranged on the rough screens, the outer diameters of the fine screens are identical to the inner diameter of the fluidized bed cylinder, the aperture of the fine screens is smaller than grain sizes of the catalyst particles carried on the fine screens, a raw material inlet pipe is arranged at the bottom of the fluidized bed, and a reaction product outlet pipe is arranged at the top of the fluidized bed.
Description
Technical field
The present invention relates to a kind of multicompartment fluidized bed and application process thereof that is used for the phenolic compound alkylated reaction, be specially adapted to produce continuously alkylphenol compounds.
Background technology
Phenolic compound (comprising phenol, metacresol, paracresol, orthoresol and other phenol system compound etc.) can generate alkylphenol compounds through alkylated reaction.
The phenolic compound that has phenyl ring, its non-occupy-place carbon atom all might be connected an alkyl, generate the different alkylate of alkyl number, so the alkylation of phenolic compound is a very complicated reaction.Such as, through alkylated reaction, 2 or 6 on the paracresol phenyl ring connect a tert-butyl group, generate the 2-Butylated Hydroxytoluene; On the paracresol phenyl ring 2 and 6 whiles respectively connect a tert-butyl group, just generate 2, the 6-BHT.Connect the alkylated reaction of an alkyl, be called the monoalkylation reaction; Connect the alkylated reaction of 2 or 2 above alkyl, be called many alkylated reactions.Monoalkylation reaction and many alkylated reactions usually take place simultaneously, are difficult to control.Different phenol is through monoalkylation reaction and many alkylated reactions; Can obtain a variety of alkyl phenols; Different alkyl phenols has different use; All be the important chemical product, be widely used in production fields such as chemical assistant, plastics, rubber, medicine, essence and flavoring agent, oil product, synthetic material.
The commercial production alkyl phenol is in the presence of catalyst, to carry out alkylated reaction to phenolic compound with alkylating agent.Catalyst commonly used is strong-acid ion exchange resin, atlapulgite etc., and alkylating agent commonly used has isobutene, the tert-butyl alcohol, methyl tertiary butyl ether(MTBE), oligomerisation butylene etc.All the time, the most frequently used phenols alkylated reaction equipment is stirred tank.Put into stirred tank to the phenol of question response, add catalyst, stir down and be warmed up to setting value, feed alkylating agent and begin alkylated reaction, reach the extent of reaction of needs after, stop to feed alkylating agent, subsequent treatment is carried out in discharging.This is a typical intermittent reaction process, trivial operations, and labour intensity is big, and equipment efficiency of usage is low.In order to reach the reaction conversion ratio that needs, have to prolong the time of staying of reaction mass, mean residence time was generally more than 3 hours; The time of staying, long more side reaction was many more.Its subsequent treatment generally all is the rectifying column of continous way operation, for satisfying the coupling of reactor and rectifying column, has to strengthen the stirred tank size, and increases huge intermediate storage tank.If in order to mate continuous rectification process thereafter; In stirred tank, carry out continuous feeding and discharging; Change the process of suitable intermittent reaction into the continous way operation; Then can bring negative consequences such as catalyst loss, raw material short circuit, product overreaction, the time of staying that also can not significantly reduce reaction mass.
Particularly when production only increased the alkyl phenol of an alkyl, step stirred tank demonstrated beyond one's ability more.Because wherein the mean residence time of material is long, on the phenolic compounds phenyl ring, connect the just increase thereupon of chance of second or more a plurality of alkyl.Such as, in stirred tank, produce the 2-Butylated Hydroxytoluene, in the post reaction mixture, when containing about 60% (mol ratio) of major product 2-Butylated Hydroxytoluene, main byproduct 2, about 12% (mol ratio) of 6-BHT; When containing about 70% (mol ratio) of major product 2-Butylated Hydroxytoluene, main byproduct 2, about 20% (mol ratio) of 6-BHT.2,6-BHT content height brings great production capacity waste and separation difficulty.
In order to overcome the defective of stirred tank, fixed bed reactors have been developed.It is little, simple to operate that fixed bed reactors have a volume, can continuous reaction etc. advantage.But be applied to the phenols alkylation process, also demonstrate significant disadvantages.Such as, the alkylation process of phenols is significant exothermic reaction, in order to dispel the heat, in the fixed bed complicated heat abstractor must be installed; In order to improve catalyst efficiency, alkylating catalyst particle size is generally less, and the fixed bed convection cell of being made up of these granules has very big resistance, has to increase pumping power, thereby has increased energy consumption greatly.So the fixed bed alkylation reactor never is being used widely aspect the alkylated reaction of phenolic compound.
As everyone knows, fluidized-bed reactor has the reaction speed equilibrium, mass-and heat-transfer is fast, easy to operate, production efficiency is high, be easy to remarkable advantage such as continuous operation, can replace fixed bed reactors under a lot of situation and use.But; The alkylated reaction that is used for phenolic compound; Still there is wretched insufficiency in common fluid bed: if the shallow then alkylating agent of bed penetrates escape easily; When particularly using isobutene to make alkylating agent, isobutene is easy to penetrate the solid catalyst particle bed, along with reactant mixture is discharged fluid bed.The alkylating agent of these escapes can bring the fault of subsequent handling, also has hidden danger such as security against fire.Therefore, must recycle the alkylating agent of escaping.This will bring a series of trouble, such as purification that separates, reclaims alkylating agent of alkylating agent and product etc.If bed deeply then fluidisation is unstable, produce defectives such as the conversion rate of products fluctuation is big, catalyst is taken out of seriously, local dead bed.Thereby the domestic so far instance that does not also have fluidized-bed reactor to be used for the commercial production alkylphenol compounds.
In sum, develop efficient novel alkylation reactor, it is necessary to be used for carrying out continuous operation phenols alkylated reaction.
Summary of the invention
The present invention is intended to overcome the deficiency of prior art, and novel alkylation reactor of a kind of efficient multicompartment fluidized bed and application process thereof are provided, and carries out continuous operation phenolic compound alkylated reaction.
The object of the invention is realized through following technical proposals:
A kind of multicompartment fluidized bed that is used for the phenolic compound alkylated reaction; It is characterized in that compound baffle plate constitutes described compound baffle plate horizontal positioned more than 2 layers by placing in the fluid bed cylindrical shell; Its circumferential edges is contacted with the inwall of fluid bed cylindrical shell; Each compound baffle plate top is exactly a relatively independent compartment, and each compartment is all independently loaded catalyst granules, constitutes the one-level fluid bed; Described compound baffle plate is constructed as follows: its bottom is the horizontal comb that is welded to form by some short tubes, the internal communication of described short tube, and these short tube one ends are communicated with the water inlet standpipe, and the other end is communicated with the water outlet riser interiors and firm welding; Be one deck wide-meshed screen above the horizontal comb, the external diameter of wide-meshed screen is consistent with the fluid bed cylinder internal diameter; Be one deck fine screen mesh above the wide-meshed screen, the external diameter of fine screen mesh is consistent with the fluid bed cylinder internal diameter; The particle diameter of the little catalyst granules that carries on it in the aperture of fine screen mesh; The fluid bed bottom is provided with the material inlet pipeline, and the top is provided with the reacting product outlet pipeline.
Above-mentioned multicompartment fluidized bed is used to carry out the application process of the continuous alkylated reaction of phenolic compound; On each compound baffle plate, load catalyst granules respectively; Phenolic compound raw material and alkylating agent are sent into fluid bed from the fluid bed bottom through the material inlet pipeline continuously, and reacted product is discharged fluid bed from the fluid bed top through the reacting product outlet pipeline continuously.
The invention has the advantages that, adopt the MULTILAYER COMPOSITE baffle plate to form multicompartment fluidized bed, reduced the time of staying of material in reactor, effectively reduced the generation of side reaction; Every laminarization bed can be controlled catalyst average grain diameter and catalyst loading amount respectively in the multicompartment fluidized bed, has effectively stablized fluidized state, has avoided the material channel to penetrate the product composition instability that bed causes; By the compound baffle plate that horizontal comb, wide-meshed screen, fine screen mesh are formed, not only stop the catalyst granules between different baffle plates to mix mutually, also can accurately control reaction temperature through circulation heat transfer medium in horizontal comb; All compound baffle plates fit together through standpipe, can dismantle baffle plate easily, also can be easily catalyst changeout more.Realize continuous operation phenols alkylated reaction effectively, solved the intermittent reaction trivial operations, in the time of problem such as labour intensity is big, and equipment efficiency of usage is low, mean residence time is long, reduced energy consumption, had practical value.
Description of drawings
Fig. 1 is a structural representation of the present invention, is one 2 laminarization bed shown in the figure.Among Fig. 1: the 1st, the fluid bed cylindrical shell, the 2nd, advance the water standpipe, the 3rd, material inlet pipeline, the 4th, reacting product outlet pipeline, the 5th, water outlet standpipe, the 6th, fine screen mesh, the 7th, wide-meshed screen, the 8th, horizontal comb; S1 is phenolic compound and alkylating agent, and S2 is a product; L1 is the heat transfer medium that flows into, and L2 is the heat transfer medium that flows out.
Fig. 2 is compound baffle arrangement sketch map; Wherein, the 1st, the fluid bed cylindrical shell, the 2nd, advance the water standpipe, the 5th, water outlet standpipe, the 6th, fine screen mesh, the 7th, wide-meshed screen, the 8th, horizontal comb.
Fig. 3 is the structural representation of horizontal comb; Among Fig. 3, the 2nd, advance the water standpipe, the 5th, water outlet standpipe, the 8th, horizontal comb.
The specific embodiment
Referring to Fig. 1, Fig. 2; The object of the invention is realized through following technical proposals: a kind of multicompartment fluidized bed that is used for the phenolic compound alkylated reaction; Compound baffle plate constitutes more than 2 layers by placing in the fluid bed cylindrical shell 1 cylindraceous; Described compound baffle plate horizontal positioned, its circumferential edges is contacted with the inwall of fluid bed cylindrical shell, and each compound baffle plate top is exactly a relatively independent compartment; Each compartment is all independently loaded catalyst granules, constitutes the one-level fluid bed; Described compound baffle plate is constructed as follows: its bottom is the horizontal comb 8 that is welded to form by some short tubes, the internal communication of described short tube, these short tube one ends and water inlet standpipe 2 internal communication, the other end and water outlet standpipe 5 internal communication and firm welding; These short tubes and standpipe also have the effect of cooling of internal circulation heat transfer medium or intensification except supporting role.Be one deck wide-meshed screen 7 above the horizontal comb, the external diameter of wide-meshed screen is consistent with the fluid bed cylinder internal diameter; The aperture of wide-meshed screen is bigger than the aperture of fine screen mesh, mainly plays a supportive role.The wire diameter of forming wide-meshed screen possesses enough intensity greater than 1 millimeter, can support the fine screen mesh 6 on it.Be one deck fine screen mesh 6 above the wide-meshed screen, the external diameter of fine screen mesh is consistent with the fluid bed cylinder internal diameter; The particle diameter of the little catalyst granules that carries on it in the aperture of fine screen mesh guarantees that catalyst granules can be through the flow of pore of fine screen mesh.Fluid bed cylindrical shell bottom is provided with material inlet pipeline 3, and fluid bed cylindrical shell top is provided with reacting product outlet pipeline 4.
Distance between described 2 layers of compound baffle plate is 1 times to 4 times of fluid bed cylinder internal diameter, and the distance between these compound baffle plates is the same, and is perhaps different.Baffle group integral body is put into the fluid bed cylindrical shell from above.When baffle group (the MULTILAYER COMPOSITE baffle plate that promptly connects) when putting into the fluid bed cylindrical shell, on each compound baffle plate, load the appropriate amount of catalysts particle respectively.The catalyst granules static height of being loaded is 1/5th to 1/2nd of place compartment height.
Referring to Fig. 3, the structure of described compound baffle plate is: described water inlet standpipe 2 has two respectively with water outlet standpipe 5, and the water inlet standpipe connects outside inlet channel, and the water outlet standpipe connects outside outlet conduit; Its bottom is horizontal comb 8, is welded to form by some short tubes, and all short tubes all are internal communication, these short tubes again with 4 standpipes (refer to above-mentioned two the water inlet standpipes, two water outlet standpipes) internal communication and firm welding.These short tubes and standpipe also have the effect of inner water flowing cooling or intensification except supporting role.
The application process of above-mentioned multicompartment fluidized bed; Baffle group integral body is put into the fluid bed cylindrical shell from above; On each compound baffle plate, load the appropriate amount of catalysts particle respectively; The catalyst granules static height of being loaded is 1/5th to 1/2nd of place compartment height; Be used for carrying out the continuous alkylated reaction of phenolic compound: phenolic compound raw material and alkylating agent are sent into fluid bed from the fluid bed bottom through the material inlet pipeline continuously, and reacted product is discharged fluid bed from the fluid bed top through the reacting product outlet pipeline continuously.
Described phenolic compound raw material is any one of phenol or metacresol or paracresol or orthoresol or cresols.
Described alkylating agent is any one of isobutene or the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) or oligomerisation butylene.
Described catalyst granules is strong-acid ion exchange resin particle or atlapulgite particle.The particle diameter of described atlapulgite is 0.5-2.0mm; The particle diameter of strong-acid ion exchange resin alive is 0.4-1.25mm.
During operation; Phenolic compound and alkylating agent fluid-mixing S1 feed fluid bed from the multicompartment fluidized bed bottom; Flow from bottom to top through each compound baffle plate, make catalyst granules fluidised formization, phenolic compound and alkylating agent generation alkylated reaction simultaneously; Generate alkylphenol compounds, the product S2 of generation and unreacted raw material are flowed out by multicompartment fluidized bed top.Feed intake control phenolic compound molal quantity greater than the alkylating agent molal quantity, let the alkylating agent total overall reaction, leave like this in the product of fluid bed and just do not contain unreacted alkylating agent.
More than in the process of reaction, can make the heat transfer medium L1 of inflow easily through water inlet standpipe, water outlet standpipe and horizontal comb, the heat transfer medium L2 of outflow circulates, and utilizes the temperature control reaction temperature that flows into heat transfer medium.Heat transfer medium is a water, or glycerine.
During use; On every layer of compound baffle plate, catalyst granules is arranged all; Catalyst granules average grain diameter on every layer of compound baffle plate is greater than the fine screen mesh aperture on compound baffle plate of this layer and the compound baffle plate of last layer; Catalyst granules just can not flow between every layer of compartment, and liquid material or gas-liquid mixed material can flow freely through the fine screen mesh aperture of compound baffle plate.
Use the multicompartment fluidized bed of said MULTILAYER COMPOSITE baffle plate composition, can carry out the alkylated reaction of phenolic compound continuously, efficiently, reposefully.When the mixed material of phenolic compound and alkylating agent composition got into multicompartment fluidized bed, because each bed is all superficial, fluidized state was good, did not have channel and dead bed generation; From top to bottom, along with constantly carrying out of alkylated reaction, the content of alkylating agent can constantly reduce, and when material upwards leaves the highest point bed, has no longer contained unreacted alkylating agent.
With a fluid bed cylindrical shell cylindraceous, wherein place 5 layers of compound baffle plate, each compound baffle plate is made up of horizontal comb, wide-meshed screen, fine screen mesh, from top to bottom, according to the order of horizontal comb, wide-meshed screen, fine screen mesh, installs firm.All compound baffle plates all are to link together through 4 standpipes (comprising into water standpipe 2 and water outlet standpipe 5), form baffle group jointly.All horizontal comb and standpipes of forming baffle group, inside all is communicated with, the whole fluid bed cylindrical shell of putting into from above.When baffle group is put into the fluid bed cylindrical shell, on each compound baffle plate, all place catalyst granules, the static height of layer of catalyst particles equals 1/2nd of fluid bed cylinder internal diameter.2 two of standpipes of water inlet connect outside inlet channel, and 5 two of water outlet standpipes connect outside outlet conduit, and what flow in the water-in and water-out pipeline is the heat transfer medium propane diols.All compound baffle plate horizontal positioned, its circumferential edges is contacted with the inwall of fluid bed cylindrical shell, and the distance between two compound baffle plates equals 4 times of fluid bed cylinder internal diameter, just forms a relatively independent compartment on each compound baffle plate; Be filled with catalyst granules above the compound baffle plate, different bed catalyst granules particle mean sizes equate.A kind of 5 laminarization bed bioreactors have so just been constituted.
The normal pressure continued operation is made alkylating agent with methyl tertiary butyl ether(MTBE), and phenol is raw material, carries out alkylated reaction, produces 2,4, the 6-tri-butyl-phenol; Raw material and alkylating agent are sent into through feed pipe from the multicompartment fluidized bed bottom continuously, and reacted material is discharged through discharge nozzle from top continuously.
Catalyst is a granule active clay, particle diameter 0.5-2.0mm; Rate of charge (molal quantity) methyl tertiary butyl ether(MTBE): phenol=2.8:1.0; Reaction temperature is 150 ℃ in the fluid bed; Mean residence time 0.5 hour (mean residence time refers to that material rests on the average time in the multicompartment fluidized bed of the present invention, below herewith); Contain major product 2,4 in the material of outflow fluidized-bed reactor, 6-tri-butyl-phenol 85% (mol ratio), main byproduct 6-tert-butyl phenol 3% (mol ratio).
With a fluid bed cylindrical shell cylindraceous, wherein place 6 layers of compound baffle plate, each compound baffle plate is made up of horizontal comb, wide-meshed screen, fine screen mesh, from top to bottom, according to the order of horizontal comb, wide-meshed screen, fine screen mesh, installs firm.All compound baffle plates all are to link together through 4 standpipes (comprising into water standpipe 2 and water outlet standpipe 5), form baffle group jointly.All horizontal comb and standpipes of forming baffle group, inside all is communicated with, the whole fluid bed cylindrical shell of putting into from above.When baffle group is put into the fluid bed cylindrical shell, on each compound baffle plate, all place catalyst granules, the static height of layer of catalyst particles equals 1/5th of fluid bed cylinder internal diameter.2 two of standpipes of water inlet connect outside inlet channel, and 5 two of water outlet standpipes connect outside outlet conduit, and heat transfer medium uses propane diols.All compound baffle plate horizontal positioned, its circumferential edges is contacted with the inwall of fluid bed cylindrical shell, and the distance between per two compound baffle plates equals 1 times of fluid bed cylinder internal diameter, just forms a relatively independent compartment on each compound baffle plate; Be filled with catalyst granules above the compound baffle plate, different bed catalyst granules particle mean sizes equate.A kind of 6 laminarization bed bioreactors have so just been constituted.
The normal pressure continued operation is made alkylating agent with the oligomerisation butylene, and phenol is raw material, carries out alkylated reaction, produces 2,4,6-trioctylphosphine phenol; Raw material and alkylating agent are sent into through the material inlet pipeline from the multicompartment fluidized bed bottom continuously, and reacted material is discharged from top through the reacting product outlet pipeline continuously.
Catalyst is a granule active clay, particle diameter 0.5-2.0mm; Rate of charge (molal quantity) oligomerisation butylene: phenol=2.5:1.0; 150 ℃ of reaction temperatures; Mean residence time 0.6 hour; Contain major product 2,4 in the material of outflow fluidized-bed reactor, 6-trioctylphosphine phenol 78% (mol ratio), main byproduct 6-octyl phenol 5% (mol ratio).
With a fluid bed cylindrical shell cylindraceous, wherein place 4 layers of compound baffle plate, each compound baffle plate is made up of horizontal comb, wide-meshed screen, fine screen mesh, from top to bottom, according to the order of horizontal comb, wide-meshed screen, fine screen mesh, installs firm.All compound baffle plates all are to link together through 4 standpipes (comprising into water standpipe 2 and water outlet standpipe 5), form baffle group jointly.All horizontal comb and standpipes of forming baffle group, inside all is communicated with, the whole fluid bed cylindrical shell of putting into from above.When baffle group is put into the fluid bed cylindrical shell, on each compound baffle plate, all place catalyst granules, the static height of layer of catalyst particles equals 1/3rd of fluid bed cylinder internal diameter.2 two of standpipes of water inlet connect outside inlet channel, and 5 two of water outlet standpipes connect outside outlet conduit, and heat transfer medium uses propane diols.All compound baffle plate horizontal positioned, its circumferential edges is contacted with the inwall of fluid bed cylindrical shell, and the distance between per two compound baffle plates equals 3 times of fluid bed cylinder internal diameter, just forms a relatively independent compartment on each compound baffle plate; Be filled with catalyst granules above the compound baffle plate, different bed catalyst granules particle mean sizes equate.A kind of 4 laminarization bed bioreactors have so just been constituted.
The normal pressure continued operation is made alkylating agent with the tert-butyl alcohol, and orthoresol is a raw material, carries out alkylated reaction, produces 4-tert-butyl o cresols; Raw material and alkylating agent are sent into through the material inlet pipeline from the multicompartment fluidized bed bottom continuously, and reacted material is discharged from top through the reacting product outlet pipeline continuously.
Catalyst is the NKC-9 strong-acid ion exchange resin that Chemical Plant of Nankai Univ. produces, particle diameter 0.4-1.25mm; Rate of charge (molal quantity) tert-butyl alcohol: orthoresol=0.98:1.00; 110 ℃ of reaction temperatures; Mean residence time 0.3 hour; Contain major product 4-tert-butyl o cresols 80% (mol ratio) in the material of outflow fluidized-bed reactor, main byproduct 4,6-di-t-butyl orthoresol 3% (mol ratio).
With a fluid bed cylindrical shell cylindraceous, wherein place 2 layers of compound baffle plate, each compound baffle plate is made up of horizontal comb, wide-meshed screen, fine screen mesh, from top to bottom, according to the order of horizontal comb, wide-meshed screen, fine screen mesh, installs firm.All compound baffle plates all are to link together through 4 standpipes (comprising into water standpipe 2 and water outlet standpipe 5), form baffle group jointly.All horizontal comb and standpipes of forming baffle group, inside all is communicated with, the whole fluid bed cylindrical shell of putting into from above.When baffle group is put into the fluid bed cylindrical shell, on each compound baffle plate, all place catalyst granules, the static height of layer of catalyst particles equals 1/3rd of fluid bed cylinder internal diameter.2 two of standpipes of water inlet connect outside inlet channel, and 5 two of water outlet standpipes connect outside outlet conduit, and heat transfer medium uses propane diols.All compound baffle plate horizontal positioned, its circumferential edges is contacted with the inwall of fluid bed cylindrical shell, and the distance between per two compound baffle plates equals 2 times of fluid bed cylinder internal diameter, just forms a relatively independent compartment on each compound baffle plate; Be filled with catalyst granules above the compound baffle plate, different bed catalyst granules particle mean sizes equate.A kind of 2 laminarization bed bioreactors have so just been constituted.
The normal pressure continued operation is made alkylating agent with isobutene, and metacresol is a raw material, carries out alkylated reaction, produces 6-tert-butyl group metacresol; Raw material and alkylating agent are sent into through the material inlet pipeline from the multicompartment fluidized bed bottom continuously, and reacted material is discharged from top through the reacting product outlet pipeline continuously.
Catalyst is the NKC-9 strong-acid ion exchange resin that Chemical Plant of Nankai Univ. produces, particle diameter 0.4-1.25mm; Rate of charge (molal quantity) isobutene: metacresol=0.98:1.00; 110 ℃ of reaction temperatures; Mean residence time 0.2 hour; Contain major product 6-tert-butyl group metacresol 76% (mol ratio) in the material of outflow fluidized-bed reactor, main byproduct 4,6-di-t-butyl metacresol 2% (mol ratio).
With a fluid bed cylindrical shell cylindraceous, wherein place 3 layers of compound baffle plate, each compound baffle plate is made up of horizontal comb, wide-meshed screen, fine screen mesh, from top to bottom, according to the order of horizontal comb, wide-meshed screen, fine screen mesh, installs firm.All compound baffle plates all are to link together through 4 standpipes (comprising into water standpipe 2 and water outlet standpipe 5), form baffle group jointly.All horizontal comb and standpipes of forming baffle group, inside all is communicated with, the whole fluid bed cylindrical shell of putting into from above.When baffle group is put into the fluid bed cylindrical shell, on each compound baffle plate, all place catalyst granules, the static height of layer of catalyst particles equals 1/3rd of fluid bed cylinder internal diameter.2 two of standpipes of water inlet connect outside inlet channel, and 5 two of water outlet standpipes connect outside outlet conduit, and heat transfer medium uses propane diols.All compound baffle plate horizontal positioned, its circumferential edges is contacted with the inwall of fluid bed cylindrical shell, and the distance between per two compound baffle plates equals 2 times of fluid bed cylinder internal diameter, just forms a relatively independent compartment on each compound baffle plate; Be filled with catalyst granules above the compound baffle plate, different bed catalyst granules particle mean sizes equate.A kind of 3 laminarization bed bioreactors have so just been constituted.
The normal pressure continued operation is made alkylating agent with isobutene, and paracresol is a raw material, carries out alkylated reaction, generates Butylated Hydroxytoluene; Raw material and alkylating agent are sent into through the material inlet pipeline from the multicompartment fluidized bed bottom continuously, and reacted material is discharged from top through the reacting product outlet pipeline continuously.
Catalyst is the NKC-9 strong-acid ion exchange resin that Chemical Plant of Nankai Univ. produces, particle diameter 0.4-1.25mm; Rate of charge (molal quantity) isobutene: paracresol=0.99:1.00; 110 ℃ of reaction temperatures; Mean residence time 0.3 hour; Contain major product 2-Butylated Hydroxytoluene 78% (mol ratio) in the material of outflow fluidized-bed reactor, main byproduct 2,6-BHT 2% (mol ratio).
With a fluid bed cylindrical shell cylindraceous, wherein place 3 layers of compound baffle plate, each compound baffle plate is made up of horizontal comb, wide-meshed screen, fine screen mesh, from top to bottom, according to the order of horizontal comb, wide-meshed screen, fine screen mesh, installs firm.All compound baffle plates all are to link together through 4 standpipes (comprising into water standpipe 2 and water outlet standpipe 5), form baffle group jointly.All horizontal comb and standpipes of forming baffle group, inside all is communicated with, the whole fluid bed cylindrical shell of putting into from above.When baffle group is put into the fluid bed cylindrical shell, on each compound baffle plate, all place catalyst granules, the static height of layer of catalyst particles equals 1/3rd of fluid bed cylinder internal diameter.2 two of standpipes of water inlet connect outside inlet channel, and 5 two of water outlet standpipes connect outside outlet conduit, and heat transfer medium uses propane diols.All compound baffle plate horizontal positioned, its circumferential edges is contacted with the inwall of fluid bed cylindrical shell, and the distance between per two compound baffle plates equals 2 times of fluid bed cylinder internal diameter, just forms a relatively independent compartment on each compound baffle plate; Be filled with catalyst granules above the compound baffle plate, different bed catalyst granules particle mean sizes equate.A kind of 3 laminarization bed bioreactors have so just been constituted.
The normal pressure continued operation is made alkylating agent with isobutene, and cresols is a raw material, carries out alkylated reaction, generates a tert-butyl group cresols; Raw material and alkylating agent are sent into through the material inlet pipeline from the multicompartment fluidized bed bottom continuously, and reacted material is discharged from top through the reacting product outlet pipeline continuously.
Catalyst is the NKC-9 strong-acid ion exchange resin that Chemical Plant of Nankai Univ. produces, particle diameter 0.4-1.25mm; Rate of charge (molal quantity) isobutene: cresols=0.99:1.00; 110 ℃ of reaction temperatures; Mean residence time 0.3 hour; Contain major product 2-Butylated Hydroxytoluene, 6-tert-butyl group metacresol total 78% (mol ratio) in the material of outflow fluidized-bed reactor, main byproduct 2,6-BHT, 4,6-di-t-butyl metacresol adds up to 2% (mol ratio).
Claims (10)
1. multicompartment fluidized bed that is used for the phenolic compound alkylated reaction; It is characterized in that compound baffle plate constitutes described compound baffle plate horizontal positioned more than 2 layers by placing in the fluid bed cylindrical shell; Its circumferential edges is contacted with the inwall of fluid bed cylindrical shell; Each compound baffle plate top is exactly a relatively independent compartment, and each compartment is all independently loaded catalyst granules, constitutes the one-level fluid bed; Described compound baffle plate is constructed as follows: its bottom is the horizontal comb that is welded to form by some short tubes, the internal communication of described short tube, and these short tube one ends are communicated with the water inlet standpipe, and the other end is communicated with the water outlet riser interiors and firm welding; Be one deck wide-meshed screen above the horizontal comb, the external diameter of wide-meshed screen is consistent with the fluid bed cylinder internal diameter; Be one deck fine screen mesh above the wide-meshed screen, the external diameter of fine screen mesh is consistent with the fluid bed cylinder internal diameter; The particle diameter of the little catalyst granules that carries on it in the aperture of fine screen mesh; The fluid bed bottom is provided with the material inlet pipeline, and the top is provided with the reacting product outlet pipeline.
2. according to the power 1 described multicompartment fluidized bed that is used for the phenolic compound alkylated reaction, it is characterized in that the wire diameter of forming wide-meshed screen is greater than 1 millimeter.
3. according to the power 1 described multicompartment fluidized bed that is used for the phenolic compound alkylated reaction, it is characterized in that the distance between described 2 layers of compound baffle plate is 1 to 4 times of fluid bed cylinder internal diameter.
4. according to the power 1 described multicompartment fluidized bed that is used for the phenolic compound alkylated reaction; It is characterized in that; Load catalyst granules respectively on described each compound baffle plate, the catalyst granules static height of being loaded is 1/5th to 1/2nd of place compartment height.
5. according to the power 1 described multicompartment fluidized bed that is used for the phenolic compound alkylated reaction, it is characterized in that described water inlet standpipe and water outlet standpipe have two respectively.
6. weigh the application process that 1 said multicompartment fluidized bed is used to carry out the continuous alkylated reaction of phenolic compound; It is characterized in that; On each compound baffle plate, load catalyst granules respectively; Phenolic compound raw material and alkylating agent are sent into fluid bed from the fluid bed bottom through the material inlet pipeline continuously, and reacted product is discharged fluid bed from the fluid bed top through the reacting product outlet pipeline continuously.
7. according to power 6 described application processes, it is characterized in that described phenolic compound raw material is any one of phenol or metacresol or paracresol or orthoresol or cresols.
8. according to power 6 described application processes, it is characterized in that described alkylating agent is any one of isobutene or the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) or oligomerisation butylene.
9. according to power 6 described application processes, it is characterized in that described catalyst is atlapulgite or strong-acid ion exchange resin.
10. according to power 9 described application processes, it is characterized in that the particle diameter of described atlapulgite is 0.5-2.0mm; The particle diameter of strong-acid ion exchange resin alive is 0.4-1.25mm.
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| CN112479877A (en) * | 2020-12-21 | 2021-03-12 | 江苏极易新材料有限公司 | Synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate |
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| US5379705A (en) * | 1992-11-11 | 1995-01-10 | Kawasaki Jukogyo Kabushiki Kaisha | Fluidized-bed incinerator |
| CN1229782A (en) * | 1998-03-19 | 1999-09-29 | 化学工业部西北化工研究院 | Phenol compounds synthetized 2,3,6-trimethyl phenol catalyst and its tech. |
| CN101507907A (en) * | 2008-02-15 | 2009-08-19 | 旭化成化学株式会社 | Temperature control method of fluidized bed reactor |
| CN101804314A (en) * | 2010-05-12 | 2010-08-18 | 新奥新能(北京)科技有限公司 | Fluidized bed reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5379705A (en) * | 1992-11-11 | 1995-01-10 | Kawasaki Jukogyo Kabushiki Kaisha | Fluidized-bed incinerator |
| CN1229782A (en) * | 1998-03-19 | 1999-09-29 | 化学工业部西北化工研究院 | Phenol compounds synthetized 2,3,6-trimethyl phenol catalyst and its tech. |
| CN101507907A (en) * | 2008-02-15 | 2009-08-19 | 旭化成化学株式会社 | Temperature control method of fluidized bed reactor |
| CN101804314A (en) * | 2010-05-12 | 2010-08-18 | 新奥新能(北京)科技有限公司 | Fluidized bed reactor |
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| CN112479877A (en) * | 2020-12-21 | 2021-03-12 | 江苏极易新材料有限公司 | Synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate |
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