CN1268500A - Toluene disproportionation and transalkylation method - Google Patents

Toluene disproportionation and transalkylation method Download PDF

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CN1268500A
CN1268500A CN99113576A CN99113576A CN1268500A CN 1268500 A CN1268500 A CN 1268500A CN 99113576 A CN99113576 A CN 99113576A CN 99113576 A CN99113576 A CN 99113576A CN 1268500 A CN1268500 A CN 1268500A
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toluene
tower
hydrocarbon
transalkylation
toluene disproportionation
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CN1084321C (en
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孔德金
李华英
邹薇
郭宏利
玩畋
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Abstract

The present invention relates to a prodn. method of benzene and C8 aromatic hydrocarbon by toluene disproportionation and translkylation reaction. Under the condition of hydroforming and reaction on bismuth oxide-contained zeolite catayst, the reaction distillate is a mixture of C6-C10 hydrocarbon and paraffinic hydrocarbon below C5. After separation of distillate, benzene and C8A are discharged, toluene cycle. C9A flow and indan-contained xylene column liquid or heavy aromatic hydrocarbon top liquid are converged and enter the reaction zone. Advantages include no loss of C9A raw material, high allowable indan content, high C10A utilization rate, no discharge of C11 hydrocarbon etc.

Description

Toluene disproportionation and transalkylation method
The present invention relates to toluene disproportionation and transalkylation method.
Along with the world can utilize being becoming tight day deficient day by day, the energy of crude resources, refining of petroleum is faced with stern challenge.In order fully to effectively utilize resource, in the crude oil deep processing, done extensive and fruitful research and discovery.In recent years, along with the application and the development of Materials science, plastics, synthon and China Synthetic Rubber Industry have obtained fast development, and market is to the demand sustainable growth of benzene and dimethylbenzene.Though in petroleum cuts reformation and cracking process, can obtain a large amount of benzene,toluene,xylenes and C 9 +A raw materials such as (C9 aromatic and above hydrocarbon thereof), but this approach of simple dependence obtains benzene and dimethylbenzene also far can not satisfy the demand in market, and in the aroamtic hydrocarbon raw material that obtains, narrow, commercially available cheap toluene of range of application and C 9A (C9 aromatic) content has accounted for 40~50% of aromatic hydrocarbons total amount.Toluene is carried out disproportionation reaction generate benzene and dimethylbenzene and toluene and C 9 +A carries out transalkylation and generates the operational path of dimethylbenzene, the exploration of new catalyst, has become the great research topic of petrochemical industry.Up to now, many countries are in the world utilizing toluene, C 9A and C 10 +Hydrocarbon (carbon ten and above hydrocarbon thereof) is produced benzene and number of research projects has been carried out in the dimethylbenzene aspect, existing kinds of processes industrialization.Owing to be subjected to the restriction of catalyst performance,, still exist many problems at the yield of utilization ratio of raw materials, purpose product and the aspects such as consumption of energy.
In petroleum chemical industry, the core of various Technologies is catalyst technologies.Article one, very sophisticated operational path tends to change because of the invention of a raw catalyst.According to levels of catalysts and technical process in the past, with toluene and C 9A is a main raw material, uses fixed-bed reactor, and reaction generates C under the mordenite catalyst existence condition 6~C 9Aromatic hydrocarbons, C 1~C 5Alkane and a small amount of C 10 +Hydrocarbon.Toluene and C in the reaction overhead product 9A circulates fresh toluene and the fresh C external with the battery limit (BL) after separating 9A converges the back as reactor feed.Owing to be subjected to the restriction of catalyst performance, the C that device itself generates 10 +Hydrocarbon can not circular treatment, C 10 +Hydrocarbon can only be discharged out-of-bounds, and utilization ratio of raw materials is not high, and the fresh C that out-of-bounds comes 9The strict control of palpus IND (indane) content wherein is lower than 0.3% to guarantee the IND content in the reactor aromatic feed among the A.Because boiling point and the C of IND 9The boiling point of the trimethylbenzene among the A (TMB) is very approaching, therefore provides the disproportionation device fresh C 9The C of the heavy aromatics column overhead of A 9The content of IND need be lower than 1.0% usually among the A, to satisfy this processing requirement.Above-mentioned technology can cause in the tower still liquid effluent and contain about 5~15% C 9A discharges at the bottom of the heavy aromatics Tata and can not make full use of.
Transalkylation catalyst, reaction mass composition and reaction conditions have been described among U.S. Pat 2795629, US3551510, US3701813 and the US3729521.The catalyzer patent that is used for alkyl transfering process has US2795629, US3780122 and US3849340.In fact above patent can not make full use of C owing to be subjected to the influence of catalyst performance 9A and above hydrocarbon thereof, the yield of purpose product is all lower, uses on full scale plant, and its material consumption, energy consumption are very big, and economic and technical norms are uneconomical.
The exploitation of a petrochemical process and to improve be because succeeding in developing with improving constantly of its performance of associated catalysts promotes after all.In order to improve disproportionation device processing toluene and C 9The ability of A, reduce device energy consumption and material consumption, reach the working condition requirement of scale economics, people have developed the catalyst for toluene disproportionation and transalkylation of high-speed and high conversion in succession.But, along with the raising of catalyzer transformation efficiency, the C of generation 10The amount of above heavy aromatics has also increased, thereby has caused the decline of purpose selectivity of product.
US4341914 has at first proposed to use C on the basis of above-mentioned technology 10A round-robin alkyl transfering process suppresses C 10The generation of hydrocarbon, thus purpose product benzene and C improved 8The selectivity of A, its technical process as shown in Figure 1.
Fig. 1 carries out C in the US4341914 document 10A round-robin process flow diagram.
1 is benzenol hydrorefining among Fig. 1, and 2 is the heavy aromatics tower, and 3 is toluene disproportionation and transalkylation reaction zone, and 4 is the benzene tower, and 5 is toluene tower, and 6 is benzenol hydrorefining, and 8 is C 8 +A (containing indane, C8 aronmatic and C9 aromatic and above hydrocarbon thereof) raw material charging, 9 is the fresh feed toluene feed, and 10 are circulation toluene, and 11 is the benzene discharging, and 12 is C 8The A discharging, 17 is C 10 +Hydrocarbon, 18 is C 9A and C 10A.
In fact above-mentioned technology be made up of first Disengagement zone, reaction zone and second Disengagement zone. First Disengagement zone comprises benzenol hydrorefining 1 and 2 liang of Tower Systems of heavy aromatics tower; Reaction zone comprises reactor, high pressure knockout drum and stripper; Second Disengagement zone is made up of benzene tower 4, toluene tower 5 and benzenol hydrorefining 6 three towers. Its characteristics are: (1) can carry out part and all circulations of product benzene, improves C8The productive rate of A; (2) utilize C10The circulation of A improves C8The productive rate of A. Yet, when after the circulation of carrying out benzene with the decrease reaction raw materials in the conversion ratio of toluene, thereby make above-mentioned technology only be suitable for high C9The reaction raw materials of A concentration (〉=50%). Generally, C in the reaction raw materials9The concentration of A is the concentration that is lower than toluene, and therefore, the circulation of benzene should not be adopted for most factories. In addition, owing to be subjected to the restriction of catalyst service condition, must strict control raw material C8 +Indane among the A is brought the amount of reactor into, namely must the strict control first fractionation zone heavy aromatics tower 2 cat head C9Indane content is less than 1% among the A, thus with the indane more than 50% from its tower reactor with C10 +Hydrocarbon is discharged out-of-bounds. Because indane and C9The boiling point of TMB among the A (trimethylbenzene) is very approaching, can cause the heavy aromatics tower reactor to discharge in the liquid in control heavy aromatics column overhead indane content and contain 5~15% C9A is with C10 +Hydrocarbon is discharged out-of-bounds from tower reactor. In addition because C10 +Hydrocarbon is discharged out-of-bounds from benzenol hydrorefining 6 bottoms, just C9The C that A and partial reaction generate10A returns into reaction zone by the lateral line withdrawal function of benzenol hydrorefining 6, therefore, and the C that this technology has just partly utilized transalkylation itself to generate10 +Hydrocarbon, and raw material C8 +C in the A raw material10 +Hydrocarbon can't obtain utilizing, and C8 +Part C in the A raw material9A is with C10 +Hydrocarbon is discharged out-of-bounds.
The objective of the invention is the strict demand C that exists in the above-mentioned document in order to overcome 9Indane content can not surpass 1% in the charging of A raw material, need lose portion C for separating indane 9A raw material, and raw material C 8 +C among the A 10 +Hydrocarbon also can not get the shortcoming than good utilisation, and a kind of toluene disproportionation and transalkylation novel method are provided, and this method has permission indane content height in the raw material charging, C 9The free of losses of A raw material, C 10The A raw material availability is high and possess all heavy aromaticss and the C that digestion self produces 8 +C among the A 10 +The ability of hydrocarbon, the C in the reactor feed raw material 10 +Hydrocarbon content can reach 15% (weight), and C does not discharge in system 11 +The characteristics of hydrocarbon.
The objective of the invention is to realize by following technical scheme: a kind of toluene disproportionation and transalkylation method may further comprise the steps successively:
A) contain the raw material C of indane, C8 aronmatic and C9 aromatic and above hydrocarbon thereof 8 +A separates in first disengaging zone earlier, and first disengaging zone is made of benzenol hydrorefining, isolates the C8 aronmatic material at the benzenol hydrorefining cat head, and tower still material contains indane and C9 aromatic and above hydrocarbon C thereof 9 +A;
B) the above-mentioned first disengaging zone dimethylbenzene Tata still material and toluene material being entered with the bismuth oxide zeolite is the toluene disproportionation and the transalkylation reaction zone of catalyzer, generates toluene disproportionation and the transalkylation reaction zone logistics that is rich in benzene and C8 aronmatic under transalkylation conditions;
C) above-mentioned toluene disproportionation is separated in second disengaging zone with the transalkylation reaction zone logistics, isolates benzene, toluene and dimethylbenzene by benzene tower, toluene tower and benzenol hydrorefining successively, and it is rich in the C of C9 aromatic and above hydrocarbon thereof 9 +After the benzenol hydrorefining tower bottoms of A converges with aforementioned toluene disproportionation and transalkylation reaction zone reaction raw materials, together as toluene disproportionation and transalkylation reaction zone raw material.
In the technique scheme, the isolated toluene in second disengaging zone partly or entirely is recycled into toluene disproportionation and transalkylation reaction zone, and isolated benzene also can partly loop back reaction zone, is beneficial to improve C 8The productive rate of A, but because can reduce the transformation efficiency of toluene in the reaction raw materials simultaneously, therefore also can not circulate, directly as product, discharge out-of-bounds; Isolated dimethylbenzene can be discharged out-of-bounds after isolating o-Xylol again in second disengaging zone.Used zeolite is mordenite, ZSM-5 zeolite or β zeolite in toluene disproportionation and the transalkylation reaction zone, and its preferred version is mordenite or beta-zeolite.A heavy aromatics tower also can be arranged in first disengaging zone in the technique scheme, contain the raw material C of indane, C8 aronmatic and C9 aromatic and above hydrocarbon thereof 8 +A isolates the C8 aronmatic material through the benzenol hydrorefining cat head, and tower still material enters the heavy aromatics tower to be separated.The heavy aromatics column overhead is isolated indane, C9 aromatic and carbon ten hydrocarbon, and wherein by weight percentage, indane is 0~5%, and carbon ten hydrocarbon are 0~50%, and the tower still is discharged carbon 11 and above hydrocarbon thereof, and the cat head material is as toluene disproportionation and transalkylation reaction zone reaction raw materials.In the raw material that enters toluene disproportionation and transalkylation reaction zone, toluene and C 9The part by weight of A is 90/10~10/90.
Key of the present invention has been to use the zeolite catalyst of bismuth oxide, make the reactivity worth of catalyzer improve greatly, reduced the restriction of catalyzer, made the content of indane in the raw material allow to reach 0~5% (weight), therefore at C indane content in the reaction raw materials 8 +Bring a small amount of indane that comes in the A raw material into and just need not its major part to be removed C when so also just having avoided the separation indane by the heavy aromatics tower 9The loss of A raw material.Same because used the zeolite catalyst of bismuth oxide, make this catalyzer have C simultaneously 10 +The function of hydrocarbon hydrodealkylation, thereby C 10 +Hydrocarbon itself just can be used as raw material and circulates, and need not to discharge out-of-bounds from heavy aromatics tower still, has improved C 10 +The utilization ratio of hydrocarbon has obtained effect preferably.This catalyzer also has the ability that generates high-purity o dimethylbenzene in addition, helps the high-quality C of the p-Xylol (PX) of production high density after separating o-Xylol 8A is significant for the production of PX.Utilize the hydrodealkylation function of bismuth oxide zeolite catalyst, system has been possessed digest all heavy aromaticss and the C that self produces 8 +C among the A 10 +The ability of hydrocarbon makes the tower bottoms of benzenol hydrorefining of second disengaging zone can directly be recycled into toluene disproportionation and transalkylation reaction zone.C in the reactor feed 10 +Hydrocarbon content can allow to reach 20% (weight), and need not C 11 +Hydrocarbon has been obtained effect preferably to out-of-bounds discharging.
Fig. 2 is toluene disproportionation of the present invention and alkyl transfering process schematic diagram.
Among Fig. 2,1 is benzenol hydrorefining, and 2 is the heavy aromatics tower, and 3 is toluene disproportionation and transalkylation reaction zone, and 4 is the benzene tower, and 5 is toluene tower, and 6 is benzenol hydrorefining, and 7 is ortho-xylene column, and 8 is C8 +A (containing indane, C8 aronmatic and C9 aromatic and above hydrocarbon thereof) raw material charging, 9 is the fresh feed toluene feed, and 10 are circulation toluene, and 11 is the benzene discharging, and 12 is C8The A discharging, 13 is C8The discharging of A liquid, 14 for ortho-xylene column ejects material, and 15 is the discharging of heavy aromatics column overhead, and 16 is the discharging of heavy aromatics Tata still, and 19 is benzenol hydrorefining 6 tower reactor out-feed liquids, and 20 is the tower reactor out-feed liquid of benzenol hydrorefining 1, and 21 is ortho-xylene tower reactor liquid.
This technology is made up of first Disengagement zone, second Disengagement zone and toluene disproportionation and transalkylation reaction zone three parts. First Disengagement zone is made up of benzenol hydrorefining 1 and heavy aromatics tower 2. Second Disengagement zone forms (do not adopt ortho-xylene such as device, ortho-xylene column 7 can not established yet) by benzene tower 4, toluene tower 5 and benzenol hydrorefining 6 and ortho-xylene column 7. Reaction zone 3 comprises the compositions such as charging surge tank, reactor, high pressure knockout drum and stripper. The distillate of reaction zone at first enters benzene tower 4, and cat head distillates that benzaldehyde product 11 drains into out-of-bounds or the part circulation enters reaction zone. The tower bottoms of benzene tower 4 enters toluene tower 5, after the isolated toluene cycle stock 10 of cat head converges with fresh toluene material 9, together as the reaction zone toluene feed. The tower bottoms of toluene tower 5 enters in the benzenol hydrorefining 6. Extract C at benzenol hydrorefining 6 cats head8The cat head C of A liquid 13 and benzenol hydrorefining 18A liquid 12 converges rear discharge out-of-bounds. According to specific requirement, if need to produce ortho-xylene, then can establish ortho-xylene column 7. At this moment, the liquid of top of the tower 13 of benzenol hydrorefining 6 is not directly discharged out-of-bounds, but enters ortho-xylene column 7, comes the ortho-xylene 21 of production high-quality. After the tower bottoms of benzenol hydrorefining 6 tower bottoms 19 and the first Disengagement zone benzenol hydrorefining 1 or the liquid of top of the tower of heavy aromatics tower 2 and fresh toluene charging 9 and circulation toluene 10 mix, directly enter reaction zone, react.
The detailed technology route of this toluene disproportionation and transalkylation new method is:
A) contain indane, C8A、C 9 +The C of A8 +The A raw material separates in first Disengagement zone earlier, isolates C at the first knockout tower cat head8A material, tower reactor material directly enter reaction zone and react;
B) with the separating obtained logistics in above-mentioned first Disengagement zone, with the isolated toluene of the fresh toluene that out-of-bounds comes and second Disengagement zone and C9 +After the A cycle stock converges, under hydro condition, enter toluene disproportionation and transalkylation reaction zone 3 take containing metal bismuth oxidate zeolite as catalyst, by toluene disproportionation and transalkylation reaction, generate and be rich in benzene and C8The toluene disproportionation of A and transalkylation reaction zone logistics;
C) above-mentioned toluene disproportionation is separated in second Disengagement zone with the transalkylation reaction zone effluent, through benzene tower 4, toluene tower 5 is isolated benzene, toluene, and according to market and requirement of actual working condition, can ortho-xylene column 7 be set in the back of the benzenol hydrorefining 6 of second Disengagement zone, produce highly purified ortho-xylene (OX), benzenol hydrorefining 6 tower reactors are discharged and are rich in C9Heavy aromatics (the C of A9 +A)。
In the technique scheme, in initial reaction stage, because system is still unstable, or at last stage reaction, because a large amount of cokings of catalyst, the first Disengagement zone heavy aromatics tower 2 can be enabled, to heat up in a steamer C8 +C in the A raw material11 +The impurity such as hydrocarbon and micro-S, N. Like this, benzenol hydrorefining 1 tower bottoms enters heavy aromatics tower 2. Its tower reactor is discharged C11 +Hydro carbons, cat head distillate indane, C9A and C10Hydrocarbon, wherein by weight percentage, indane is 0~5%, C10Hydrocarbon is 0~50%, and tower reactor is discharged C11 +Hydrocarbon. The isolated toluene in second Disengagement zone is capable of circulation as the charging of reaction zone raw material, and isolated benzene also can partly loop back reaction zone, is beneficial to improve C8The productive rate of A, but meanwhile can reduce the conversion ratio of toluene in the reaction raw materials, therefore can not circulate yet, directly as product, discharge out-of-bounds; The isolated C that is rich in of the second Disengagement zone benzenol hydrorefining, 6 tower reactors9Heavy aromatics (the C of A9 +A) no longer enter first Disengagement zone, after converging with the first Disengagement zone first knockout tower benzenol hydrorefining, 1 tower bottoms or first Disengagement zone heavy aromatics tower 2 liquid of top of the tower, under hydro condition, directly enter reactor as reactor feed. In the raw material that enters toluene disproportionation and transalkylation reaction zone, toluene and C9The part by weight of A is 90/10~10/90, and the used zeolite of catalyst is at least a in modenite, ZSM-5 zeolite or the beta-zeolite.
The present invention is further elaborated below by specific embodiment.[embodiment 1~5]
Carry out toluene and be rich in C with fixed-bed reactor 9The raw material of A carries out disproportionation and the transalkylation reaction performance is investigated.25 millimeters of reactor inside diameter φ, 1000 millimeters of length, stainless steel.The equal up and down 3 millimeters granulated glass spherees of filling φ of beds play air-flow and distribute and supporting role, the mordenite catalyst of filling 20 gram bismuth oxides in the reactor.Aroamtic hydrocarbon raw material (toluene and C 9 +A) with after hydrogen mixes pass through beds from top to bottom, carry out toluene disproportionation and transalkylation reaction, generate benzene and C 8A and a spot of C 5Following non-aromatics.
Raw material toluene and C 9 +A derives from petrochemical complex Aromatic Hydrocarbon United Plant, H 2Be electrolysis hydrogen, through dehydrating processing, reaction result is listed in the table 1.The data processing formula is as follows:
Data processing is counted by weight percentage, and formula is as follows:
Figure A9911357600081
Figure A9911357600082
Figure A9911357600083
* 100% (weight)
Figure A9911357600086
Figure A9911357600087
Figure A9911357600088
Raw materials used composition and reaction result thereof see table 1 for details.
Table 1 toluene be rich in C 9The raw material of A is formed and reaction result
Embodiment ????1 ????2 ????3 ????4 ????5
Temperature of reaction, ℃ reaction pressure, MPa WHSV, hr -1Hydrogen hydrocarbon mol ratio ????340 ????3.0 ????2.0 ????5 ????380 ????3.0 ????2.0 ????5 ????390 ????3.0 ????2.5 ????8 ????420 ????3.0 ????3.0 ????10 ????480 ????4.0 ????4.5 ????15
Reactor feed forms % by weight ??C 1~C 5Non-aromatics benzene toluene C 8A ??C 9NA ??C 9A ??C 10 +The hydrocarbon indane adds up to ????0.00 ????0.26 ????88.82 ????1.29 ????0.00 ????5.32 ????4.11 ????0.20 ????100.00 ????0.00 ????0.00 ????56.97 ????1.07 ????0.98 ????34.22 ????5.70 ????1.06 ????100.00 ????0.00 ????0.00 ????55.00 ????1.00 ????0.98 ????33.01 ????8.51 ????1.50 ????100.00 ????0.00 ????0.00 ????36.24 ????0.63 ????0.94 ????45.05 ????15.00 ????2.14 ????100.00 ????0.00 ????0.00 ????10.60 ????0.50 ????1.10 ????65.50 ????18.27 ????4.03 ????100.00
Reaction liquid product composition % by weight ??C 1~C 5Non-aromatics benzene toluene C 8A ??oX ??C 9NA ??C 9A indane C 10 +Hydrocarbon adds up to ????0.97 ????17.90 ????52.00 ????22.86 ????4.92 ????0.00 ????2.51 ????0.00 ????3.76 ????100.00 ????2.37 ????7.50 ????37.14 ????32.33 ????6.96 ????0.10 ????16.06 ????0.05 ????4.45 ????100.00 ????2.58 ????7.18 ????36.46 ????32.42 ????6.97 ????0.10 ????16.49 ????0.05 ????4.72 ????100.00 ????2.61 ????5.09 ????28.94 ????33.11 ????7.13 ????0.10 ????19.62 ????0.05 ????10.48 ????100.00 ????2.65 ????3.64 ????20.92 ????33.47 ????7.20 ????0.10 ????25.58 ????0.05 ????13.59 ????100.00
Liquid yield *, (weight) ????0.9650 ????0.9600 ????0.9364 ????0.9271 ????0.9176
Annotate *: liquid yield is meant the weight of the reaction liquid product that every gram reaction raw materials obtains, C after reaction 9NA is carbon nine non-aromaticss.According to the data of embodiment in the table 12, the reaction result that calculates embodiment 2 is:
Toluene conversion 37.42%
C 9A transformation efficiency 54.94%
Total conversion rate 43.99%
IND transformation efficiency 95.47%
Generate benzene selective 17.95%
Generate C 8A selectivity 74.70%
The o-Xylol purity 98.58% of extraction
From table 1 data as can be seen, along with the change of raw material composition and the variation of reaction conditions, benzene amount and C in the reaction product 8The A amount all has significantly to be increased, and the C of the higher concentration of bringing in the raw material 9 +Hydrocarbon all has significantly decline.And, C in the product 8The ratio of A/ benzene is along with C in the raw material 10 +The increase of hydrocarbon and increasing.Illustrate that the used catalyzer of the present invention has good conversion C 9 +The selectivity of hydrocarbon ability and high yield dimethylbenzene.Analyze embodiment 1~5 and respectively organize data, as can be seen, there is a trim point in this system entails, promptly enters the C of reactor 9 +The hydrocarbon amount (comprises fresh material C 9 +Hydrocarbon amount and recycle stream C 9 +Hydrocarbon amount sum) C that equals to react away 9 +The hydrocarbon amount with go out the benzenol hydrorefining 6 tower stills C that promptly circulates 9 +The hydrocarbon amount.At this moment, enter the fresh C of this system 9 +Hydrocarbon will be transformed fully, and whole Aromatic Hydrocarbon United Plant is also with not extraction heavy aromatics.

Claims (5)

1, a kind of toluene disproportionation and transalkylation method may further comprise the steps successively:
A) contain the raw material C of indane, C8 aronmatic and C9 aromatic and above hydrocarbon thereof 8 +A separates in first disengaging zone earlier, and first disengaging zone is made of benzenol hydrorefining, isolates the C8 aronmatic material at the benzenol hydrorefining cat head, and tower still material contains indane and C9 aromatic and above hydrocarbon C thereof 9 +A;
B) the first disengaging zone dimethylbenzene Tata still material and toluene material being entered with the bismuth oxide zeolite is the toluene disproportionation and the transalkylation reaction zone of catalyzer, generates toluene disproportionation and the transalkylation reaction zone logistics that is rich in benzene and C8 aronmatic under transalkylation conditions;
C) above-mentioned toluene disproportionation is separated in second disengaging zone with the transalkylation reaction zone logistics, isolates benzene, toluene and dimethylbenzene by benzene tower, toluene tower and benzenol hydrorefining successively, and it is rich in the C of C9 aromatic and above hydrocarbon thereof 9 +After the benzenol hydrorefining tower bottoms of A converges with aforementioned toluene disproportionation and transalkylation reaction zone reaction raw materials, together as toluene disproportionation and transalkylation reaction zone raw material.
2, according to described toluene disproportionation of claim 1 and transalkylation method, it is characterized in that isolated benzene partly is recycled into toluene disproportionation and transalkylation reaction zone in second disengaging zone, isolated toluene partly or entirely is recycled into toluene disproportionation and transalkylation reaction zone.
3,, it is characterized in that isolated dimethylbenzene is discharged out-of-bounds again in second disengaging zone after isolating o-Xylol according to described toluene disproportionation of claim 1 and transalkylation method.
4, according to described toluene disproportionation of claim 1 and transalkylation method, it is characterized in that also having a heavy aromatics tower in first disengaging zone, contain the raw material C of indane, C8 aronmatic and C9 aromatic and above hydrocarbon thereof 8 +A, isolate the C8 aronmatic material through the benzenol hydrorefining cat head, tower still material enters the heavy aromatics tower to be separated, the heavy aromatics column overhead is isolated indane, C9 aromatic and carbon ten hydrocarbon, wherein by weight percentage, indane is 0~5%, and carbon ten hydrocarbon are 0~50%, the tower still is discharged carbon 11 and above hydrocarbon thereof, and the cat head material is as toluene disproportionation and transalkylation reaction zone reaction raw materials.
5,, it is characterized in that used zeolite is mordenite, ZSM-5 zeolite or β zeolite according to described toluene disproportionation of claim 1 and transalkylation method.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318359C (en) * 2004-07-12 2007-05-30 中国石油化工股份有限公司 Process for toluene disproportionation and alkyl transfer
CN103845915A (en) * 2014-02-15 2014-06-11 中山大学 Multi-stage flash evaporation separation equipment of toluene disproportionation reaction effluent and separation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4341914A (en) * 1980-12-22 1982-07-27 Uop Inc. Transalkylation process with recycle of C10 hydrocarbons
US5321183A (en) * 1992-03-12 1994-06-14 Mobil Oil Corp. Process for the regioselective conversion of aromatics to para-disubstituted benzenes
CN1050594C (en) * 1996-08-20 2000-03-22 中国石油化工总公司 Methylbenzene disproportionating and alkyl group transfering process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318359C (en) * 2004-07-12 2007-05-30 中国石油化工股份有限公司 Process for toluene disproportionation and alkyl transfer
CN103845915A (en) * 2014-02-15 2014-06-11 中山大学 Multi-stage flash evaporation separation equipment of toluene disproportionation reaction effluent and separation method thereof

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