CN1506341A - Transalkylation process between benzene and C9 arene - Google Patents

Transalkylation process between benzene and C9 arene Download PDF

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CN1506341A
CN1506341A CNA021511675A CN02151167A CN1506341A CN 1506341 A CN1506341 A CN 1506341A CN A021511675 A CNA021511675 A CN A021511675A CN 02151167 A CN02151167 A CN 02151167A CN 1506341 A CN1506341 A CN 1506341A
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benzene
zeolite
transalkylation
arene
weight
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CN1216020C (en
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程文才
孔德金
杨德琴
李华英
邢宇
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to transalkylation process between benzene and C9 arene. Inside solid-gas phase fixed bed reactor, under the hydrogenating condition and at 300-600 deg.c and 1.0-6.0 MPa, the materials benzene and C9 arene with arene weight space velocity 0.5-3.0 /hr and hydrogen/hydrocarbon molar ratio 2-10 are reacted to produce toluene, C8 arene and C1-C5 paraffin hydrocarbon. The present invention adopts hydrogen type zeolite catalyst carrying Bi and at least one metal or oxide of Fe, Co, Ni, Cr, Zr, W, La, Le and Ag. The said technological process is especially suitable for transalkylation between benzene and C9 arene and may be used in industrial production.

Description

Benzene and carbon nonaarene transalkylation method
Technical Field
The invention relates to a benzene and carbon nonaromatic hydrocarbon transalkylation method, in particular to a method for preparing toluene and xylene by benzene and carbon nonaromatic hydrocarbon transalkylation.
Background
It is known that toluene disproportionation or toluene and C9Aromatic disproportionation and transalkylation are a process for interconversion of aromatics with the aim of adjusting benzene, toluene, xylene and C by this technique9Supply-demand balance between aromatics. Usually, toluene and C are present in most regions9Excess aromatics, and deficiency of benzene and xylene. Therefore, toluene disproportionation or toluene and C are employed in most regions9Aromatic disproportionation and alkyl transfer process for removing C and toluene9The conversion of aromatics to benzene and xylenes is why the majority of the aromatics complexes in the world today have disproportionation and transalkylation units. In the late eighties of the twentieth century, the process for preparing p-xylene and benzene by selective disproportionation of toluene (MSTDP) by Mobil corporation in the United states is industrialized (CHEMICALENGINEERING/DECEMBER1989, 83). The concentration of p-xylene (PX) in the xylene generated by the toluene selective disproportionation reaction is up to 82-87%, even more than 90%. The PX concentration in the dimethylbenzene is very high, so that the equipment for separating the PX is miniaturized, the operation cost is low, and the selective disproportionation process of the methylbenzene is widely concerned by people. However, since the chemical reaction formula of the process is two moles of toluene disproportionation to produce 1 mole of benzene and 1 mole of xylene:
a typical product distribution in industry is a benzene/xylene molar ratio of 1.44/1, producing about 0.46 tons of benzene and 0.44 tons of xylene per 1 ton of toluene converted [ アロマテイツクス (aromatic), 1995, 47(1, 2): 40 to 48]. That is, the plant using the MSTDP process is undoubtedly ten for countries and regions where benzene consumption is largeProper classification is carried out; however, in some countries and regions, the benzene consumption is low, the demand of the xylene is high, and the yield of the xylene is expected to be high and low. In this case, the selective disproportionation process of toluene may result in over-demand of benzene, and if the yield of xylene is increased, the benzene will be overstocked. Benzene and C of the present invention9An aromatic hydrocarbon transalkylation process, which is a method for solving the problems that benzene is over-supply and xylene is under-supply. The process is particularly useful in plants where there is a high demand for xylene and a low demand for benzene, and where a selective disproportionation process of toluene is desired, or in countries or regions where benzene is in excess and xylene is in deficiency. Excess benzene for reaction with C9The aromatics are subjected to transalkylation to produce toluene and xylene, and the toluene is used as a raw material ofa toluene selective disproportionation process to produce benzene and xylene rich in p-xylene, so that the aim of producing more xylene is fulfilled.
Benzene and C9The single-pass conversion rate of the aromatic hydrocarbon transalkylation reaction is as high as 55-70%, the miniaturization of equipment is facilitated, the circulation quantity of raw materials is reduced, the energy consumption is reduced, and the single-pass conversion rate of the toluene disproportionation and transalkylation reaction is 40-48%.
Benzene and C9The process for transalkylation of aromatic hydrocarbons is particularly suitable for the transalkylation of toluene and C9The aromatic hydrocarbon raw material and the factory with the toluene selective disproportionation process have the areas with large xylene demand and small benzene demand. Thus, toluene is used as a raw material, benzene and xylene rich in p-xylene are produced by a toluene selective disproportionation device, a part of the benzene is sold as a product, and a part of the benzene is used for benzene and C9The aromatics are subjected to transalkylation to produce toluene and xylene, so that the aims of producing less benzene and producing more xylene are fulfilled.
Chinese patent application 01105840.4 discloses a method for transalkylation of benzene and heavy aromatics with benzene and C10Aromatic hydrocarbon or/and C11Aromatic hydrocarbon is used as raw material, and reacts to generate toluene, xylene and C9Aromatic hydrocarbons and C1～C5A paraffinic hydrocarbon.
Disclosure of Invention
The invention aims to solve the technical problems that the prior art has poor conversion flexibility of aromatic hydrocarbon, needs toluene as a raw material for producing dimethylbenzene and can additionally produce a large amount of benzene, and provides a novel benzene and C9An aromatic transalkylation process. The method uses benzene and C9The aim of producing toluene and xylene products is fulfilled by taking aromatic hydrocarbon as a raw material through transalkylation reaction, so that high flexibility of processing the raw material and high flexibility of the product are realized, and the market demand is met.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: benzene and C9Aromatic transalkylation process with benzene and C9The arene is taken as a raw material to carry out transalkylation reaction to generate toluene and C8Aromatic hydrocarbons and C1～C5The reaction conditions are as follows:
a) under the hydrogen condition, the raw materials of benzene and C9The aromatic hydrocarbon is contacted with catalyst by gas-solid phase fixed bed reactor, and benzene and C are9The weight ratio of the aromatic hydrocarbon is 10-90: 90-10, the reaction temperature is 300-600 ℃, the reaction pressure is 1.0-6.0 MPa, and the weight space velocity of the raw material is 0.5-3.0 hours-1The hydrogen-hydrocarbon molar ratio is 2-10;
b) the catalyst comprises 10-90 parts by weight of hydrogen-containing zeolite and SiO of zeolite2/Al2O3The molar ratio is 3-500, 0.05-10 parts of bismuth-loaded metal or/and oxide is loaded on zeolite, and 10-60 parts of binder alumina is contained in the catalyst.
In the above technical scheme, C9The aromatic hydrocarbon is at least one selected from trimethylbenzene, methyl ethylbenzene or propyl benzene, C8The aromatic hydrocarbon is xylene, ethylbenzene or their mixture, C1～C5The paraffinic hydrocarbons of (a) are methane, ethane, propane, butane or/and pentane. SiO of the zeolite used2/Al2O3The molar ratio is preferably 10 to 100, more preferably 10 to 30. The zeolite is at least one selected from mordenite, Beta zeolite, Y zeolite, ZSM-5 zeolite, MCM-22 zeolite, MCM-49 zeolite or MCM-56 zeolite, preferably selected from mordenite and/or Beta zeolite. Metal or oxygen of bismuth in parts by weightThe preferable range of the compound is 0.1 to 5.0 parts. The zeolite is also loaded with at least one metal or/and oxide selected from iron, cobalt, nickel, chromium, zirconium, tungsten, lanthanum, rhenium or silver, and the weight portion of the metal or/and the oxide is 0.1-10 parts, and the preferable range is 0.1-5 parts.
Benzene and C of the present invention9The main reactions of the aromatic transalkylation reaction are as follows:
the invention adopts hydrogen type zeolite containing bismuth as catalyst, benzene and C9Aromatic hydrocarbon is used as raw material, and the reaction raw materials of benzene and C are effectively reacted by transalkylation reaction9The aromatic hydrocarbon is converted into the dimethylbenzene, so that the flexibility of raw material processing is realized, the conversion rate of the aromatic hydrocarbon reaches 64.8%, the selectivity reaches 90%, and a better technical effect is achieved.
Benzene and C for use in the present invention9Reaction raw materials of benzene and C for aromatic hydrocarbon transalkylation process9Aromatic hydrocarbons (C)9A) All come from petrochemical industry arene complex.
The performance evaluation of the transalkylation reaction of the aromatic hydrocarbon raw material is carried out by using a fixed bed reactor, the inner diameter phi of the reactor is 20 mm, the length is 1200 mm, and the reactor is made of a stainless steel pipe. The electric heating is adopted, and the temperature is automatically controlled. The bottom of the reactor is filled with 5 mm glass beads, the reaction zone is filled with 20 g of catalyst, and the upper part is filled with 5 mm glass beads for preheating and vaporizing raw materials. Starting materials benzene and C9A is mixed with hydrogen and passes through the reactor from top to bottom to generate transalkylation reaction, and then toluene, ethylbenzene, xylene and a small amount of alkanes such as methane, ethane, propane, butane or/and pentane are generated. The process uses hydrogen, on one hand, the side reaction-the hydrodealkylation reaction of aromatic hydrocarbon needs to consume the hydrogen, and on the other hand, the hydrogen is mainly present for inhibiting the carbon deposition of the catalyst so as to prolong the running period of the catalyst. The side reaction, namely the hydrodealkylation reaction of the aromatic hydrocarbon is not large, so that the actual hydrogen consumption of the process is low.
The catalyst used in the method of the invention can be prepared according to the method of Chinese patent ZL 97106719.8.
Benzene and C9The aromatic transalkylation reaction data are processed according to the following formula:
the invention is furtherillustrated by the following examples.
Detailed Description
[ example 1]
With benzene/C9A weight ratio of about 40/60, benzene and C were reacted in the presence of hydrogen over a hydrogen mordenite catalyst containing 0.5% by weight bismuth9A transalkylation reaction, raw material aromatic hydrocarbon weight space velocity WHSV 1.5 hours-1The hydrogen-hydrocarbon molar ratio is 6.0, the reaction pressure is 1.5MPa, the reaction temperature is 385 ℃, and the reaction raw material composition and the liquid product composition are as follows, in weight percent:
NA B T C8A C9A C10A IND
feedstock 0.0539.510.040.0359.170.510.69
Liquid product 0.9721.4130.4328.3015.263.560.06
In the table, NA-non-aromatic, B-benzene, T-toluene, C8A-C8Aromatic hydrocarbons, including ethylbenzene and xylenes,
C9A-C9aromatic hydrocarbons, including trimethylbenzene, methylethylbenzene, propylbenzene, IND-indane
And (3) reaction results:
benzene conversion 47.98% (by weight)
C9Conversion of A75.24% (by weight)
Total conversion 64.33% (by weight)
Toluene + C8A Selectivity 88.82% (by weight)
[ example 2]
With benzene/C9A weight ratio of about 60/40, benzene and C were reacted in the presence of hydrogen over a zeolite Beta catalyst in the hydrogenform containing 0.1 wt% bismuth, 0.1 wt% lanthanum and 0.8 wt% tungsten9A transalkylation reaction, raw material aromatic hydrocarbon weight space velocity WHSV 3.0 hr-1The hydrogen-hydrocarbon molar ratio is 3.0, the reaction pressure is 3.0MPa, the reaction temperature is 400 ℃, and the composition of the reaction raw materials and the composition of the liquid product are as follows, in percentage by weight:
NA B T C8A C9A C10A IND
feedstock 0.0659.500.060.0239.560.340.46
Liquid product 0.8035.7027.1025.308.562.510.03
And (3) reaction results:
benzene conversion 41.80% (by weight)
C9A conversion 79.00% (by weight)
Total conversion 56.70% (by weight)
Toluene + C8A Selectivity 90.35% (by weight)
[ example 3]
With benzene/C9A weight ratio of about 30/70, benzene and C were reacted in the presence of hydrogen over a hydrogen MCM-22 zeolite catalyst containing 0.3 wt% bismuth and 0.5 wt% lanthanum9A transalkylation reaction, raw material aromatic hydrocarbon weight space velocity WHSV 3.0 hr-1The hydrogen-hydrocarbon molar ratio is 2.0, the reaction pressure is 4.0MPa, the reaction temperature is 420 ℃, and the reaction raw materialsComposition and liquid product composition as follows,% by weight:
NA B T C8A C9A C10A IND
feedstock 0.0429.930.030.0468.570.590.80
Liquid product 1.2014.0327.3831.2522.074.000.07
And (3) reaction results:
benzene conversion 55.00% (by weight)
C9A conversion 69.10% (by weight)
Total conversion 64.81% (by weight)
Toluene + C8A Selectivity 88.13% (by weight)
The conventional toluene disproportionation and transalkylation process realizes the reaction of toluene and C9A is the process of producing benzene and dimethylbenzene by raw materials; chinese patent ZL97106719.8 realizes the purpose of using toluene and C through the disproportionation and transalkylation process of toluene and heavy aromatics9A、C10A is the process of producing benzene and xylene with raw materials. Chinese patent application 01105840.4 discloses a method for transalkylation of benzene and heavy aromatics with benzene and C10Aromatic hydrocarbon or/and C11Aromatic hydrocarbon is used as raw material, and reacts to generate toluene, xylene and C9Aromatic hydrocarbons and C1～C5A paraffinic hydrocarbon. The invention passes benzene and C9Aromatic transalkylation process to effect transalkylation of benzene and C9A is the process of producing toluene and xylene with raw materials.
Usually, the method adopts a toluene disproportionation and transalkylation process or a toluene and heavy aromatic hydrocarbon disproportionation and transalkylation process to separate toluene and C9A、C10A is used for producing benzene and xylene; in special cases, i.e. when benzene is in excess and toluene and xylene are in short supply, benzene and C can be used9A transalkylation process. Thus, the invention realizes the flexibility of aromatic hydrocarbon raw materials and the flexibility of products, and can meet different requirements of the market.

Claims (8)

1. Benzene and C9Aromatic transalkylation process with benzene and C9The arene is taken as a raw material to carry out transalkylation reaction to generate toluene and C8Aromatic hydrocarbons and C1～C5The reaction conditions are as follows:
a) under the hydrogen condition, the raw materials of benzene and C9The aromatic hydrocarbon is contacted with catalyst by gas-solid phase fixed bed reactor, and benzene and C are9The weight ratio of the aromatic hydrocarbon is 10-90: 90-10, the reaction temperature is 300-600 ℃, the reaction pressure is 1.0-6.0 MPa, and the weight space velocity of the raw material is 0.5-3.0 hours-1The hydrogen-hydrocarbon molar ratio is 2-10;
b) the catalyst comprises 10-90 parts by weight of hydrogen-containing zeolite and SiO of zeolite2/Al2O3The molar ratio is 3-500, 0.05-10 parts of bismuth-loaded metal or/and oxide is loaded on zeolite, and 10-60 parts of binder alumina is contained in the catalyst.
2. Benzene and C according to claim 19Process for the transalkylation of aromatic hydrocarbons, characterized in that C9The aromatic hydrocarbon is at least one of trimethylbenzene, methyl ethylbenzene or propyl benzene.
3. Benzene and C according to claim 19Process for the transalkylation of aromatic hydrocarbons, characterized in that C8The aromatic hydrocarbon is xylene, ethylbenzene or their mixture, C1～C5The paraffinic hydrocarbons of (a) are methane, ethane, propane, butane or/and pentane.
4. Benzene and C according to claim 19Process for the transalkylation of aromatic hydrocarbons, characterised in that the SiO of the zeolite2/Al2O3The mole ratio is 10-100, and the zeolite is at least one selected from mordenite, Beta zeolite, Y zeolite, ZSM-5 zeolite, MCM-22 zeolite, MCM-49 zeolite or MCM-56 zeolite.
5. Benzene and C according to claim 49Process for the transalkylation of aromatic hydrocarbons, characterised in that the SiO of the zeolite2/Al2O3The mole ratio is 10-30, and the zeolite is selected from mordenite or/and Beta zeolite.
6. Benzene and C according to claim 19The arene alkyl transferring process features that the metal or oxide of bismuth accounts for 0.1-5.0 weight portions.
7. Benzene and C according to claim 19The arene transalkylation method is characterized in that the zeolite is also loaded with 0.1-10 parts of at least one metal or/and oxide selected from iron, cobalt, nickel, chromium, zirconium, tungsten, lanthanum, rhenium or silver by weight.
8. Benzene and C according to claim 79The arene transalkylation method is characterized in that the zeolite is loaded with 0.1-5 parts by weight of at least one metal or/and oxide selected from iron, cobalt, nickel, chromium, zirconium, tungsten, lanthanum, rhenium and silver.
CN 02151167 2002-12-11 2002-12-11 Transalkylation process between benzene and C9 arene Expired - Lifetime CN1216020C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734989B (en) * 2008-11-21 2013-10-30 中国石油化工股份有限公司 Method for selective toluene disproportionation and transalkylation of benzene and C9 aromatics
CN106488897A (en) * 2014-06-30 2017-03-08 埃克森美孚化学专利公司 The method preparing dimethylbenzene
CN108779047A (en) * 2016-03-28 2018-11-09 埃克森美孚化学专利公司 Liquid phase transfer method
CN109790083A (en) * 2016-10-04 2019-05-21 埃克森美孚化学专利公司 The de- alkyl and transalkylation of heavy arene
CN109803944A (en) * 2016-10-04 2019-05-24 埃克森美孚化学专利公司 The disproportionation and transalkylation of heavy arene

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734989B (en) * 2008-11-21 2013-10-30 中国石油化工股份有限公司 Method for selective toluene disproportionation and transalkylation of benzene and C9 aromatics
CN106488897A (en) * 2014-06-30 2017-03-08 埃克森美孚化学专利公司 The method preparing dimethylbenzene
CN108779047A (en) * 2016-03-28 2018-11-09 埃克森美孚化学专利公司 Liquid phase transfer method
CN109790083A (en) * 2016-10-04 2019-05-21 埃克森美孚化学专利公司 The de- alkyl and transalkylation of heavy arene
CN109803944A (en) * 2016-10-04 2019-05-24 埃克森美孚化学专利公司 The disproportionation and transalkylation of heavy arene

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