CN1915943A - Method for producing dimethylbenzene and benzene through dismutation of toluene and transference of alkyl - Google Patents
Method for producing dimethylbenzene and benzene through dismutation of toluene and transference of alkyl Download PDFInfo
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Abstract
This invention relates to a method for manufacturing dimethylbenzene and benzene by methylbenzene disproportionation and alkyl transfer in the presence of H2. The invention adopts an axial-radial reactor, whose axial part is on top of the radial part. A circular flange connected with the axial part of the inside distributor penetrates into the catalyst bed layer. The method takes the advantages of axial reactor and radial reactor, and can prevent the short circuit phenomenon of the gas caused by catalyst radial and axial subsidence, thus can utilize catalyst efficiently. The method can be used in dimethylbenzene industrial manufacture by methylbenzene disproportionation and alkyl transfer.
Description
Technical field
The present invention relates to a kind of toluene disproportionation and transalkylation and produce the method for dimethylbenzene and benzene.
Background technology
Dimethylbenzene is the raw material of producing p-Xylol, and p-Xylol then is one of main basic organic of petrochemical industry, in numerous chemical production field such as chemical fibre, synthetic resins, agricultural chemicals, medicine, plastics purposes is widely arranged.The maximum purposes of benzene is to produce vinylbenzene, cyclohexane and phenol, and the three accounts for 80%～90% of benzene total quantity consumed, secondly is oil of mirbane, cis-butenedioic anhydride, chlorobenzene, linear alkylbenzene etc.
Used various catalyzer are all known in the technology of toluene disproportionation and transalkylation generation dimethylbenzene and benzene and this technology.Be known that toluene disproportionation and alkyl transfering process especially, wherein disproportionation and transalkylation reaction carry out in axially-located bed or radial reactor, in the existing industrialized unit, major part has all adopted the axial restraint bed bioreactor, and the minority device has adopted radial reactor.The operational condition that this technology adopted is that the ingress temperature and pressure of reactor is respectively 200～600 ℃ and 1.5～4.5MPa, and the liquid weight air speed is 0.5～5.0 hour
-1The liquid weight air speed is meant the ratio of the weight rate of toluene and carbon nine and above aromatic hydrocarbons thereof with the gross weight of catalyzer.By this technology, adopt radial reactor, the total conversion rate of toluene and C9 aromatic is approximately greater than 40～50%, even higher, and reaches the mole selectivity greater than 94%.But after for some time, the carrying out of this technology can cause the reduction of dimethylbenzene and benzene selective and toluene and C9 aromatic total conversion rate, but the reduction of total conversion rate can be limited through improving temperature of reaction.In fact, it is aging gradually to observe catalyzer after for some time, occurs carbon laydown on catalyzer.As a result, cause that thus loss of material increases, catalyst efficiency reduces.
Dehydrogenation of ethylbenzene to styrene technology has adopted radial reactor in a large number, and the problems referred to above exist equally.In order to eliminate the shortcoming of this technology, a kind of process for manufacturing styrene is disclosed among the document CN1006061B.This processing method thinks that the various radial reactors of type are preferable described in the employing French Patent FR2365370.Because there is bad adaptability in the radial mode reactor, the easy big area of catalyzer is poisoned, and catalyst life is vulnerable to influence.Simultaneously since catalyst basket generally up to 10 meters, the fluid distribution technical requirements is very high, outer distribute tube with simplified between the gap installation time be difficult to reach design requirements, promote the use of and can cause difficulty.In order to solve the defective that the radial reactor reaction process exists, a kind of diameter of axle is disclosed among the document CN86200368U to cold-tube type ammonia synthesis converter catalyst basket, it is that beds is divided into axial direction part and radial section, wherein axial direction part be positioned at radial section above, the top cover that is about to reaction bed is opened or perforate.This reactor process, because an axial direction part is arranged at reactor catalyst bed top, so that when the obnoxious flavour composition is higher, can play a filteration, can avoid the catalyzer big area to poison, it is big to have kept radial reactor throughput simultaneously, the advantage that net value is high.In the industrial production of reality, because on the one hand along with the prolongation in reaction times, catalyzer can take place axially and natural subsidence radially, and along with the prolongation in reaction times, catalyzer also can make catalyst layer generation sedimentation because of wearing and tearing on the other hand.As time goes on, the advantage of original axial direction part catalyzer can fade away, on the contrary As time goes on and radial and axial settled aggravation, can cause the aggravation of reaction gas short circuit phenomenon, be not contact catalyst and directly run decreasing from axial direction part of reactant gases, the consequence of being brought is that reaction conversion ratio descends.
Summary of the invention
Technical problem to be solved by this invention is to use the radial reactor bad adaptability in order to overcome to exist in the above-mentioned document, the easy big area of catalyst basket is poisoned, influence catalyst life or in the past the diameter of axle in reaction process, because radial and axial sedimentation, exist reaction gas easily to cause the shortcoming of short circuit, a kind of new toluene disproportionation and the method for transalkylation production dimethylbenzene and benzene are provided.This method has the advantages that catalyst utilization height, throughput are big, catalyzer is difficult for that big area is poisoned, reaction gas can not cause short circuit.
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 toluene disproportionation and transalkylation are produced the method for dimethylbenzene and benzene, with toluene or toluene and carbon nine and above aromatic hydrocarbons thereof is raw material, with the mordenite is catalyzer, in temperature of reaction is 200～600 ℃, reaction pressure is 1.5～4.5MPa, and the liquid weight air speed is 0.5～10.0 hour
-1Under the condition, reaction generates dimethylbenzene and benzene in fixed-bed reactor, wherein fixed-bed reactor adopt axial-radial flow reactor, comprise cylindrical shell, feed-pipe, discharge nozzle, inside distributor and the outer tube that distributes, inside distributor and the outer tube that distributes form a catalyst basket, inside distributor and the outer tube that distributes have aperture in the catalyzer corresponding section, catalyst basket is divided into radial section and axial direction part two portions, axial direction part is at the catalyst basket epimere, radial section is at the catalyst basket hypomere, and radially conversion zone is positioned at the below of axial conversion zone, on the axial segmental wall of inside distributor, be connected with an annular lip of going deep into beds, wherein annular lip is goed deep into the top of beds, with the rectilineal interval of inside distributor periphery be 50% of 5 millimeters～catalyst bed layer thickness, the lower extreme point of annular lip links to each other with the junction of inside distributor radial section and axial direction part, the inseparable aperture of axial direction part portion of inside distributor.
In technique scheme, the cross-sectional shape preferred version of annular lip is parabolic type, triangular pointed, knob or straight line.The height preferable range of axial direction part is 40～1500 millimeters.Axial direction part top preferred version adopts uncovered or has the capping of many apertures.The raw material that uses promptly can be a toluene, also can be the mixture of toluene and C9 aromatic.
In the technique scheme, the concrete structure of axial-radial flow reactor is such: this reactor comprises cylindrical shell, feed-pipe, discharge nozzle, inside distributor and the outer tube that distributes, inside distributor and the outer tube that distributes form a catalyst basket, and inside distributor and the outer tube that distributes have aperture in the catalyst basket corresponding section.Catalyst basket is divided into radial section and axial direction part two portions, and wherein radial section is at the catalyst basket hypomere, and axial direction part is at the catalyst basket epimere, and it highly is 40～1500 millimeters, and preferred range is 600～1000 millimeters.On the axial segmental wall of inside distributor, be connected with an annular lip of going deep into beds, the inseparable aperture of axial direction part portion of inside distributor, the axial direction part top is adopted uncovered or is had the capping of many apertures.The cross-sectional shape of annular lip is parabolic type, triangular pointed, knob or straight line, the symmetric line in annular lip cross section can be vertical with inside distributor or becomes angle less than positive and negative 70 degree with vertical line, annular lip is goed deep into the top of beds, with the rectilineal interval of inside distributor periphery be 50% of 5 millimeters～catalyst bed layer thickness, the lower extreme point of annular lip links to each other with the junction of inside distributor radial section and axial direction part, the inseparable aperture of axial direction part portion of inside distributor.
According to a preferable embodiment of the inventive method, the liquid air speed of employing was at 1.5～2.5 hours
-1Between.
The temperature at each reactor inlet place is preferable to remain between 350～450 ℃.
The inventive method can adopt the catalyzer that is generally used for toluene disproportionation and transalkylation.With the mordenite is the catalyzer of base stock, and particularly bismuthiferous mordenite can be mentioned especially.
The method according to this invention, under 200～600 ℃ of temperature condition, and 1.5～4.5MPa pressure and 0.5～10.0 hour
-1Liquid weight-space velocity under carry out, transformation efficiency and selectivity can improve, selectivity is about more than 95% or is higher.
The present invention uses the axial-radial flow reactor after the improvement, has concentrated the advantage of axialmode reactor and radial mode reactor, has overcome their shortcoming, makes catalyzer be difficult for big area and poisons, and has improved catalyst life, has improved the effective rate of utilization of catalyzer simultaneously.In addition because the catalyst basket that adopts is divided into radial section and axial direction part two portions, make the catalyzer of axial direction part to be fully utilized, simultaneously because the existence of annular lip, continuous running along with reaction unit, even the radial and axial natural subsidence of beds takes place or because catalyst abrasion causes beds to descend, it is in good running status all the time, can not cause the short circuit phenomenon of reactant gases in the past, thus the problem of having avoided catalyst utilization to reduce.Adopt the axial-radial flow reactor after processing condition of the present invention and the above-mentioned improvement, compare to reaction process with the diameter of axle in the past, the total conversion rate of its toluene and C9 aromatic can improve, and selectivity is about 95% or higher, has obtained better technical effect.
Description of drawings
Fig. 1 is toluene disproportionation of the present invention and transalkylation technological process of production synoptic diagram.
Fig. 2 is the structure of reactor synoptic diagram.
Introduce embodiment of the present invention below so that understand the present invention better.These embodiments provide in the mode of statement, there is no the meaning of limiting protecting scope, and use above-mentioned toluene disproportionation and transalkylation Production Flow Chart as Fig. 1 to realize.
I is the feed for disproportionation pump among Fig. 1, II is a disproportionation reactor, and III is a vapour liquid separator, and VI is a stripping tower, IX is a compressor, X is the raw material surge tank, and XI is a process furnace, and XII is the reaction product air cooler, XIII is the reaction product water cooler, XIV is the stripping tower feed preheater, and XV is a stripper reboiler, and XVI is reaction feed/effluent exchanger.1 is the raw material of disproportionation and transalkylation, 2 is hydrogen make-up, 3 is circulating hydrogen, 5 are reactor feed, 6 is the reactor discharging, 7 reaction product air coolers inlet material, 8 is reaction product air cooler outlet material, 9 is the inlet feed of vapour liquid separator III, 10 are discharging gas, 11 is circulating hydrogen, and 14 is the isolated liquid in vapour liquid separator III bottom, and 15 is the stripping tower charging, 16 is stripping tower still extraction liquid, 17 is through cooled stripping tower extraction liquid, and 18 is the extraction of stripping cat head gas phase, and 19 is the extraction of stripping cat head liquid phase.
In the toluene disproportionation process flow process shown in Figure 1, toluene and C9 aromatic raw material 1 incoming stock surge tank X, enter reaction input and output material interchanger XVI by converging with recycle hydrogen 3 after circulating hydrogen compressor IX supercharging after the feedstock pump I supercharging, enter process furnace then and be heated to the required temperature of reaction, be injected into reactor II by pipeline 5 then, mixture is by radial section and axial direction part catalytic bed in this reactor.When reactor II flows out, effluent carries out heat exchange by pipeline 6 input heat exchanger XVI and raw material, draw by pipeline 7 then, respectively by behind air cooler XII and the watercooler XIII, flow into gas-liquid separator III, isolated gas major part enters circulating hydrogen compressor IX by pipeline 11 from the separator top, small part is by pipeline 10 dischargings, for keep-uping pressure and hydrogen purity, mend suitable hydrogen make-up by pipeline 2, by converging with feedstock pump I outlet liquid after the circulating hydrogen compressor supercharging.Enter stripping tower VI from the effusive liquid in knockout drum III bottom earlier with after the heat exchange of stripping tower VI tower still extraction liquid by pipeline 11, wherein by pipeline 18 dischargings, discharge by pipeline 19 by light constituent from cat head for non-condensable gas.Tower still extraction liquid is discharged by pipeline 17 after heat exchange.
24 is axial-radial flow reactor in the accompanying drawing 2, and 25 is radial section, and 26 is axial direction part, and 27 is the reaction gas opening for feed, and 28 is the outer tube that distributes, and 29 is the annular lip on the inside distributor, and 30 is the reactant discharge port, and 31 is inside distributor.
For obtaining better gas distribution effect, the gas distributor of back taper can also be installed in the inside distributor in Fig. 2.Inside distributor, the outer tube that distributes have the aperture of suitable size according to the needs that react.The height of axial direction part is generally 40～1500 millimeters, and preferable height is generally 600～1000 millimeters.Need not the special seal device between axial direction part and the radial section, simple in structure.On the axial segmental wall of inside distributor, be connected with an annular lip of going deep into beds, the inseparable aperture of axial direction part portion of inside distributor, the axial direction part top is adopted uncovered or is had the capping of many apertures.The cross-sectional shape of annular lip is parabolic type, triangular pointed, knob or straight line, the symmetric line of annular lip can be vertical with inside distributor or becomes angle less than positive and negative 70 degree with vertical line, annular lip is goed deep into the top of beds, with the rectilineal interval of interior cloth tube periphery be 50% of 5 millimeters～catalyst bed layer thickness, the lower extreme point of annular lip links to each other with the junction of inside distributor radial section and axial direction part.By above-mentioned improvement, fully guaranteed making full use of of axial direction part catalyzer.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Toluene and carbon nine and the catalyzed reaction of above aromatic hydrocarbons under hydrogen atmosphere thereof are carried out with a set of equipment, and it produces the block diagram signal as Fig. 1.Reactor adopts the reactor of Fig. 2, and the catalyzer of use adopts bismuthiferous mordenite.Reactor inside distributor diameter is 1200 millimeters, and the bed radial thickness is 800 millimeters, and static total height is 10000 millimeters.Reactor axial direction part 26 is shaped as trilateral with the flange 29 of radial section 25 in the junction of inside distributor 31, the trilateral apex angle of going deep into beds is 40 degree, the symmetric line of drift angle is perpendicular to inside distributor (being that the β angle is 0), and the vertical height of flange top and inside distributor is 100 millimeters.The temperature that reaction mass advances reactor is 360 ℃, and pressure is 3.0MPa, and the aromatic hydrocarbons flow is 22507 kilograms/hour, and reaction result sees Table 1.
[comparative example 1]
The reactor geometrical dimension is with embodiment 1, and catalyzer and reaction process condition are with embodiment 1, and just reactor axial direction part 26 does not have flange with radial section 25 in the junction of inside distributor 31 among Fig. 2.After reaction for some time, beds radially sedimentation is 20 millimeters.The reaction result of reactor sees Table 1.
[comparative example 2]
Just radially 40 millimeters of sedimentations of beds, other condition is with comparative example 1, and the reaction result of reactor sees Table 1.
[comparative example 3]
Just radially 60 millimeters of sedimentations of beds, other condition is with comparative example 1, and the reaction result of reactor sees Table 1.
As can be seen from Table 1, axial-radial flow reactor in the past is because radially sedimentation causes the reactant gases short circuit phenomenon seriously to cause transformation efficiency to descend, thereby can influence the once through yield of dimethylbenzene and benzene.
Table 1 reactor reaction result
| Component | Reactor feed | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| The flow kilogram/hour | Reactor discharging flow kilogram/hour | Reactor discharging flow kilogram/hour | Reactor discharging flow kilogram/hour | Reactor discharging flow kilogram/hour | |
| Toluene+C9 aromatic | 22395 | 12093 | 12148 | 12215 | 12373 |
| Dimethylbenzene+benzene | 90 | 9362 | 9312 | 9201 | 9010 |
| Temperature, ℃ | 360 | 372 | 371.4 | 371.0 | 370.0 |
| Pressure, MPa | 3.0 | 2.97 | 2.97 | 2.97 | 2.97 |
| Radially sedimentation, millimeter | 0 | 20 | 40 | 60 | |
| Bypass flow, kilogram/hour | 0 | 358 | 796 | 1823 | |
| Total conversion rate, % | 46.00 | 45.75 | 45.45 | 44.75 | |
Claims (4)
1, a kind of toluene disproportionation and transalkylation are produced the method for dimethylbenzene and benzene, with toluene or toluene and carbon nine and above aromatic hydrocarbons thereof is raw material, is catalyzer with the mordenite, is 200～600 ℃ in temperature of reaction, reaction pressure is 1.5～4.5MPa, and the liquid weight air speed is 0.5～10.0 hour
-1Under the condition, reaction generates dimethylbenzene and benzene in fixed-bed reactor, it is characterized in that fixed-bed reactor adopt axial-radial flow reactor, comprise cylindrical shell, feed-pipe, discharge nozzle, inside distributor and the outer tube that distributes, inside distributor and the outer tube that distributes form a catalyst basket, inside distributor and the outer tube that distributes have aperture in the catalyzer corresponding section, catalyst basket is divided into radial section and axial direction part two portions, axial direction part is at the catalyst basket epimere, radial section is at the catalyst basket hypomere, and radially conversion zone is positioned at the below of axial conversion zone, on the axial segmental wall of inside distributor, be connected with an annular lip of going deep into beds, wherein annular lip is goed deep into the top of beds, with the rectilineal interval of inside distributor periphery be 50% of 5 millimeters～catalyst bed layer thickness, the lower extreme point of annular lip links to each other with the junction of inside distributor radial section and axial direction part, the inseparable aperture of axial direction part portion of inside distributor.
2, according to the method for the described toluene disproportionation of claim 1 and transalkylation production dimethylbenzene and benzene, the cross-sectional shape that it is characterized in that annular lip is parabolic type, triangular pointed, knob or straight line.
3, according to the method for the described toluene disproportionation of claim 1 and transalkylation production dimethylbenzene and benzene, the height that it is characterized in that axial direction part is 40～1500 millimeters.
4, produce the method for dimethylbenzene and benzene according to the described toluene disproportionation of claim 1 and transalkylation, it is characterized in that the axial direction part top adopts uncovered or have the capping of many apertures.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973763A (en) * | 2017-12-08 | 2018-05-01 | 河南心连心化肥有限公司 | A kind of process units and method for preparing 2- methylfurans |
| CN115368201A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | Combined process method for toluene shape-selective disproportionation and aromatic hydrocarbon transalkylation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665258A (en) * | 1986-02-06 | 1987-05-12 | Cosden Technology, Inc. | Toluene disproportionation process |
| CN2471401Y (en) * | 2001-04-04 | 2002-01-16 | 中国石油化工股份有限公司 | Reactor for catalystic reaction |
| US6867339B2 (en) * | 2003-03-19 | 2005-03-15 | China Petroleum & Chemical Corporation | Process for producing p-xylene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973763A (en) * | 2017-12-08 | 2018-05-01 | 河南心连心化肥有限公司 | A kind of process units and method for preparing 2- methylfurans |
| CN115368201A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | Combined process method for toluene shape-selective disproportionation and aromatic hydrocarbon transalkylation |
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