CN107382647A - The method that coal-based feedstocks produce paraxylene - Google Patents

The method that coal-based feedstocks produce paraxylene Download PDF

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CN107382647A
CN107382647A CN201710575413.6A CN201710575413A CN107382647A CN 107382647 A CN107382647 A CN 107382647A CN 201710575413 A CN201710575413 A CN 201710575413A CN 107382647 A CN107382647 A CN 107382647A
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reaction
coal
catalyst
toluene
base crude
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朱志荣
李明
赵国庆
袁英
李孝慈
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Tongji University
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Abstract

The present invention relates to a kind of method of coal-based feedstocks production paraxylene.This method is using cheap coal base crude benzol and coal base crude carbinol as raw material, using external surface area is big, alkylation catalyst and anti-coking alkylated reaction medium based on weak acid and middle strong acid, pass through the processes such as pickling, weighted BMO spaces, alkylated reaction, rectifying, Crystallization Separation, isomerization reaction, transalkylation reaction and Matter Transfer, the production paraxylene of high selectivity；Selectively, methods described further comprises methylbenzene shape-selective disproportionation reaction.Alkylated reaction is carried out in fixed bed, fluid bed or moving-burden bed reactor, uses sheet MCM 56, nano whiskers ZSM 5, sheet MCM 49 or nanometer Beta molecular sieve of the catalyst for two kinds of modified metal oxides, or its compound；Isomerization, transalkylation and shape-selective disproportionation reaction also use new exclusive catalyst, are carried out in fixed bed reactors.Method provided by the present invention can effectively reduce the production cost of paraxylene, and thoroughly realize that its Non oil-based route produces.

Description

The method that coal-based feedstocks produce paraxylene
Technical field
The present invention relates to a kind of method that paraxylene is produced with coal-based feedstocks.Methods described with cheap coal base crude benzol and Coal base crude carbinol is raw material, using external surface area is big, the novel alkylation catalyst based on weak acid and middle strong acid and anti-coking Alkylated reaction medium, turned by pickling, weighted BMO spaces, alkylated reaction, rectifying, Crystallization Separation, isomerization reaction, alkyl The processes such as what Matter Transfer are moved, high selectivity is realized, produces paraxylene at low cost；Selectively, methods described is further Including methylbenzene shape-selective disproportionation reaction process.This method can thoroughly realize that the Non oil-based route of paraxylene efficiently produces.
Background technology
Paraxylene（PX）It is the aromatic hydrocarbons basic material having the call, terephthalic acid (TPA) is can obtain after its is oxidized, The latter can further synthesize important high polymer material polyester fiber and plastics.In addition, paraxylene is in medicine, agricultural chemicals, dyestuff And also there is extremely extensive purposes in the field such as solvent.According to statistics, current China PX annual requirement is up to more than 20,000,000 tons, about 12000000 tons need import.It produces heavy dependence petroleum path at present, and main technique is toluene disproportionation and xylene isomerization Separation, they are respectively present that raw material availability is low and the problem of paraxylene low yields.
China's mineral reserve are " the few oil of more coals ", and oil shortage passes through one of main bottleneck as China's industrial development, its people The sustainable and healthy development of Ji requires that China must rely on the resources advantage of itself to develop the production technology of petrochemical material, and country is really Found " using coal for replacing oil " strategy and be used as the energy and the developing direction of resource.Meanwhile China is as the coal coke place of production the biggest in the world, Coke gas and the main by-product that coal tar is coking, coke gas therefrom can extract the substantial amounts of crude benzol of recovery through further separation, and The hydrogenated cracking lighting of heavy constituent, also can obtain crude benzol in coal tar（Containing toluene）Product.With coal chemical industry in recent years Fast development, China's coking benzene production capacity is up to more than 4,000,000 tons/year, and yield is about 3,000,000 tons/year, the ratio in benzene total output Rise to nearly 30%（Other is petrobenzene）, and most of device utilization of capacity wretched insufficiency.Moreover, coking benzene be only used for cis-butenedioic anhydride, The fields such as medicine, agricultural chemicals, synthetic rubber, dyestuff, solvent, its as industrial chemicals application compared with petrobenzene also compared with It is small, it result in coking benzene price and be always less than petrobenzene, so the new way of coking benzene Transformation Application and its downstream product are opened Hair causes extensive concern both domestic and external.It is highly developed as raw material methanol technology using coal tar furnace gas, coal synthesis gas, with The a large amount of methanol devices in China in recent years to go into operation, methanol production capacity is seriously superfluous, and price persistently drops.Except preparing olefin by conversion of methanol Outside, pay close attention to the production technology that methanol synthesizes dimethylbenzene with alkylation of toluene always both at home and abroad, converted for the diversification of coal methanol Deep processing provide one it is new efficient by way of but raw material toluene still needs to obtain by petroleum path in the technique.Further, since Petrobenzene price is higher than petroleum toluene, the rare benzene of petrochemical industry circle and the research of methanol alkylation process for a long time.[Zhao Bo, Liu such as Zhao Bo The people, Tan Wei, Wu Hongyu, Guo Xinwen, petroleum journal（PETROLEUM PROCESSING）, 2013,29（4）, 605-611.] and [Yuan such as Yuan Ping Apple, Wang Hao, Xue Yanfeng, Li Yanchun, wangkai, Dong Mei, Fan Weibin, Qin Zhangfeng, Wang Jianguo, Acta PhySico-Chimica Sinica, 2016,3 (7), 1775-1784.] describe theory study in terms of methanol synthesizes toluene and dimethylbenzene catalytic reaction with oil benzene alkylation Property experiment, its content is mostly to attempt different molecular to sieve report for methanol and oil benzene alkylation reaction catalytic performance, US20110092756, CN101624327, ZL201210233696.3 and ZL201410248891.2 propose methanol and stone The simple reaction technological process of oily benzene alkylation synthesis toluene and xylene products.In a word, current existing methanol and petrobenzene In alkylated reaction or technical process, product is toluene, mixed xylenes, lighter hydrocarbons and a certain amount of heavy aromatics, and paraxylene selects Property is very low；And benzene feedstock still relies on petroleum path acquisition, its cost is higher.For the conversion of domestic coal and the spy of Chemical Industry Point, the present invention propose a kind of using cheap coal base crude benzol and coal base crude carbinol as raw material（Without separating-purifying）, using new alkane Base catalyst and anti-coking alkylated reaction medium, are converted by integrated cleaning, high selectivity, produced at low cost to two The method of toluene, it can thoroughly realize that the Non oil-based route of paraxylene efficiently produces.Although containing certain in coal base crude benzol raw material The toluene of amount and a small amount of dimethylbenzene, but have no effect on it and be combined to making for paraxylene reaction raw materials as alkyl in the present invention With it is practically free of alkaline impurities after pickling, weighted BMO spaces, and only the sulfur-bearing containing denier, nitrogenous and other impurity are to alkane The molecular sieve catalyst service life of glycosylation reaction does not form influence.
The content of the invention
The present invention is to solve current paraxylene is completely dependent on the problem of petroleum path production, there is provided a kind of cheap Coal-based feedstocks high selectivity, the method for producing paraxylene at low cost.Methods described using coal base crude benzol and coal base crude carbinol as Raw material, using with the novel alkylation catalyst that external surface area is big, acid intensity is moderate and the alkylated reaction of anti-coking Medium, pass through pickling, weighted BMO spaces, alkylated reaction, rectifying, Crystallization Separation, isomerization reaction, transalkylation reaction and thing The processes such as material circulation, produce paraxylene；Selectively, this method further comprises methylbenzene shape-selective disproportionation reaction process.
The method of a kind of coal-based feedstocks production paraxylene proposed by the present invention, using coal base crude benzol and coal base crude carbinol as original Material, by pickling, weighted BMO spaces, alkylated reaction, rectifying, Crystallization Separation, isomerization reaction and transalkylation reaction, is obtained Paraxylene；Comprise the following steps that：
（1）Coal base crude benzol is subjected to pickling and weighted BMO spaces, puts into together with coal base crude carbinol and/or successively and is alkylated instead Answer in device, while add the alkylation catalyst based on big external surface area, weak acid and middle strong acid and reaction carrier gas progress alkyl Change reaction；The mol ratio of coal base crude carbinol and coal base crude benzol is 1:1~1:6, reaction pressure is that normal pressure is warm to 5.0 MPa, reaction Spend for 350~700 DEG C, water is 1 with the mol ratio of coal base crude benzol and the total amount of coal base crude carbinol:2~10:1, gross mass air speed is 0.2~10.0 h-1；Carrier gas is 1 with the mol ratio of coal base crude benzol and the total amount of coal base crude carbinol:2~10:1；
（2）Step（1）In alkylation reaction product and unreacted benzene enter distillation system, successively through stripping tower, benzene column and Toluene tower, for the lighter hydrocarbons isolated as device fuel, the benzene isolated and part toluene are recycled into alkylation reactor conduct Reaction raw materials, the heavy component of toluene tower outflow enter PX+MX（Paraxylene+meta-xylene）Rectifying column；PX+MX rectifying columns separate The paraxylene and meta-xylene mixture gone out enters isomerization reactor, while adds isomerization catalyst, to diformazan The mol ratio of benzene and meta-xylene is 1:1~1:4, reaction pressure is normal pressure to 5.0 MPa, and reaction temperature is 250~500 DEG C, Gross mass air speed is 0.1~10.0 h-1, using H2Or N2To react carrier gas, carrier gas and paraxylene and meta-xylene it is total Mol ratio is 1:2~10:1, reaction gained mixed xylenes is recycled into PX+MX rectifying columns；The weight of PX+MX rectifying columns outflow Component raw material enters ortho-xylene rectifying column, isolated ortho-xylene；The heavy constituent material of ortho-xylene rectifying column outflow enters Enter trimethylbenzene rectifying column, separating obtained trimethylbenzene enters transalkylation reactor, toluene with the separating obtained part toluene of toluene tower Mol ratio with trimethylbenzene is 1:4~4:1, reaction pressure is normal pressure to 6.0 MPa, and reaction temperature is 350~700 DEG C, always Mass space velocity is 0.1~10.0 h-1, using H2Or N2To react carrier gas, carrier gas is with the total moles of toluene and trimethylbenzene ratio 1:2~10:1；Products therefrom and unreacting material, which together circulate, is incorporated to step（1）In alkylation reaction product, into essence Evaporate system；The heavy component material of trimethylbenzene rectifying column outflow is as device liquid fuel.
In the present invention, step（1）Coal base crude carbinol in raw material is made for the made crude carbinol of coal tar furnace gas or coal synthesis gas At least one of crude carbinol；Methanol content is 80.0 ~ 93.0 wt% in coal-based methanol raw material, other impurities component be water, At least one of dimethyl ether, ethanol, butanol or amylalcohol etc..
In the present invention, step（1）Coal base crude benzol in raw material is coking benzene, in coal tar heavy duty component lighting crude benzol extremely Few one kind；It is described also containing 0.5 ~ 15.0 wt% toluene and a small amount of dimethylbenzene and other impurities in addition to benzene in coal base crude benzol Other impurities are at least one of hexamethylene, nitrogenous or sulphur-containing substance.
In the present invention, step（1）Middle coal base crude benzol pickling uses sulfuric acid scrubbing method；Coal base crude benzole hydrogenation is pre-processed in fixation Carried out in bed reactor, using NiO-MoO3And/or Co-MoO3Catalyst.
In the present invention, step（1）In alkylation catalyst used using two kinds of modified metal oxides sheet MCM-56, Nano whiskers ZSM-5, sheet MCM-49 or nanometer Beta molecular sieves, or its compound；Two kinds of metal oxides are selected from La2O3、 CaO、Ce2O3, MgO and CuO, the content of metal oxide is 0.1 ~ 10.0 wt% in molecular sieve.
In the present invention, step（1）Described in alkylation catalyst external surface area be more than 90 m2/ g, outer surface acidity position Quantity accounts for more than the 30.0% of total acidic bit quantity, and weak acid and middle strong acid quantity account for more than the 95% of total acidic bit quantity.
In the present invention, step（1）Middle alkylated reaction carrier gas is H2Or CO2。
In the present invention, methylbenzene shape-selective disproportionation reaction is added in methods described, by step（2）Middle circulation is as reaction raw materials Toluene is sent into shape-selective disproportionation reaction device, and products therefrom and unconverted toluene are together incorporated to step（1）In alkylated reaction production In thing, into distillation system.
In the present invention, step（1）Middle alkylation reactor is anti-using fixed bed reactors, fluidized-bed reactor or moving bed Answer one kind in device.
In the present invention, isomerization, transalkylation and methylbenzene shape-selective disproportionation reaction device use fixed bed reactors.
In the present invention, isomerization reaction uses the nano-sheet ZSM- that catalyst is that metal is modified jointly with metal oxide 5th, sheet MCM-56, SAPO-5 or nanometer Beta molecular sieves, or its compound；Metal is selected from Ni, Mo or Pt, the catalyst Middle tenor is 0.01 ~ 5.0 wt%；Metal oxide is selected from Ce2O3, MgO or Fe2O3, metal aoxidizes in the catalyst Thing content is 1.0 ~ 10.0 wt%.
In the present invention, step（2）Middle transalkylation reaction is that metal is repaiied jointly with transition metal oxide using catalyst Sheet MOR, ZSM-12 of decorations, sheet Bata or SAPO-5 molecular sieve, or its compound；Metal promoter be selected from Fe, Co, Ni or Pt, tenor is 0.01 ~ 5.0 wt% in the catalyst；Transition metal oxide is selected from CuO, CdO or ZnO, described to urge Transition metal oxide content is 1.0 ~ 10.0 wt% in agent.
In the present invention, shape-selective disproportionation reaction uses the nano-sheet that catalyst is that metal is modified jointly with nonmetal oxide ZSM-5, ZSM-11, SAPO-11 or EU-1 molecular sieve；Metal is selected from Pd, Mo, Co or Ni, and tenor is in the catalyst 0.01 ~ 5.0 wt%；Nonmetal oxide is selected from B2O3、P2O5Or SiO2, nonmetal oxide content is in the catalyst 5.0 ~ 16.0 wt%。
The method of coal-based feedstocks production paraxylene in the present invention, may be selected to introduce methylbenzene shape selective disproportionation after toluene tower Reactor, improve the Feedstock treating load of whole set process.It will originally circulate to be sent into as the toluene of alkylated reaction raw material and select Shape disproportionation reactor, products therefrom and unconverted toluene, are incorporated to alkylation reaction product, together into distillation system.
The beneficial effects of the present invention are：Molecular sieve catalyst surface acid property is to influence benzene and methanol alkylation reactivity One of most important factor of energy, the acid site of weak acid and moderate strength is alkylation activity center.Tool is used in the present invention There is the novel alkylation catalyst of big external surface area and moderate strength acidity, acid intensity is adapted to, and big external surface area More acid centres are made to contribute to large-size reactant molecule or midbody product to contact and inhale with activated centre outside Attached, activation, it is catalyzed benzene and show higher activity and dimethylbenzene selective with methanol alkylation reaction.On the other hand, lead to Alkylated reaction, rectifying, Crystallization Separation, isomerization reaction, transalkylation reaction, shape-selective disproportionation reaction and Matter Transfer is crossed to wait Journey, aromatic hydrocarbons accessory substance caused by alkylated reaction is set efficiently to turn through separation, isomerization, transalkylation and selective disproportionation process Turn to paraxylene.In addition, by the pickling of coal base crude benzol, weighted BMO spaces, remove and be easily caused alkylation catalyst poisoning Impurity；Also using the alkylated reaction medium with anti-coking, i.e., with H2Or CO2To react carrier gas, and water is added in the feed, Suppression and CO of the suppression, appropriateness hydrogenation generated by system reclaimed water to Multi substituted benzenes and condensed-nuclei aromatics to alkene generation2Activation- The measures such as carbon that disappear are aoxidized, delays catalyst coking carbon distribution in alkylated reaction significantly, makes it have good reaction stability.Most Mouthful material that always wraps into for making process system in the present invention eventually is cheap coal base crude benzol and coal base crude carbinol, and output is high-purity to two Toluene product, a small amount of lighter hydrocarbons of a by-product and a small amount of heavy arene, overall reaction result show very high target product selection Property；And eliminate raw material and isolate and purify process, alkylation catalyst is changed or circulated without frequent, is truly realized non-petroleum Route, high selectivity, paraxylene is produced at low cost.
Brief description of the drawings
Fig. 1 is the typical process flow that coal-based feedstocks produce paraxylene method in the embodiment of the present invention 1.
Fig. 2 is the typical process flow that coal-based feedstocks produce paraxylene method in the embodiment of the present invention 2.
Fig. 3 is the typical process flow that coal-based feedstocks produce paraxylene method in the embodiment of the present invention 3.
Fig. 4 is the typical process flow that coal-based feedstocks produce paraxylene method in the embodiment of the present invention 4.
Fig. 5 is the typical process flow that coal-based feedstocks produce paraxylene method in the embodiment of the present invention 5.
Embodiment
Below by specific embodiment, the present invention is further described, but is not limited to this.
Embodiment 1:
Fig. 1 show the typical process flow of coal-based feedstocks production paraxylene method in the present invention.It is made thick with coal synthesis gas Methanol（90.0 wt %）, coking crude benzene（Containing 91.6 wt% benzene, 7.0 wt % toluene, 1.3 wt% dimethylbenzene and 0.1 wt% other Impurity）For raw material, wherein coking crude benzene is through sulfuric acid scrubbing, weighted BMO spaces（15wt%NiO-10wt%MoO3/ Al2O3 carriers and 10wt%Co-15wt%MoO3/ Al2O3 carried catalysts, fixed bed）Afterwards, alkylation reactor is entered with crude carbinol（Fluid bed） Catalytic reaction is carried out, it is mainly toluene, mixed xylenes, trimethylbenzene, a small amount of heavy component aromatic hydrocarbons and lighter hydrocarbons to obtain product.Above-mentioned production Thing enters distillation system in the lump, first passes around stripping tower and isolates lighter hydrocarbons, as device fuel；The heavy component warp of stripping tower outflow Benzene column, isolated unconverted benzene, circulation are used as reaction raw materials；The heavy component material of benzene column outflow is isolated through toluene tower Toluene, part toluene (20-40% ratios) circulation is as reaction raw materials；The heavy component material of toluene tower outflow is through PX+MX rectifying The isolated PX+MX of tower, it is sent to Crystallization Separation unit, crystallized isolated PX products and MX；The weight of PX+MX rectifying columns outflow Component material is through OX（Ortho-xylene）Rectifying column isolated OX, OX together enter isomerization reactor with MX obtained by crystalline element （Fixed bed）PX+MX+OX xylene mixture is converted into, the mixed material is recycled into PX+MX rectifying columns.OX rectifying column streams The heavy component material gone out separates through front three benzene column again, and gained trimethylbenzene enters transalkylation reaction with part toluene obtained by toluene tower Device（Fixed bed）, products therefrom and unreacting material together circulate and are incorporated to alkylate, into distillation system；Front three benzene column institute Heavy component is obtained as device liquid fuel.Wherein, alkylated reaction used catalyst is 2.0%La2O3It is composite modified with 1.5%CaO Sheet MCM-56 molecular sieves, external surface area is 94 m2/ g, outer surface acidity bit quantity accounts for the 35% of total acidic bit quantity, weak Acid and middle strong acidity bit quantity account for 96.1% (the temperature programming ammonia for taking conventional acidity of catalyst to determine of total acidic bit quantity Desorption method, the acidic site being desorbed before 250 DEG C are weak acid, are middle strong acid in the acidic site of 250-400 DEG C of desorption, 400 The acidic site being desorbed after DEG C is strong acid).Alkylation reaction condition is：Methanol and aromatic hydrocarbons（Benzene and toluene）Mol ratio is 1:6, reaction Pressure is normal pressure, and reaction temperature is 350 DEG C, and water is 1 with material molar ratio:2, gross mass air speed is 4.0 h-1；Using CO2For Carrier gas is reacted, carrier gas is 3 with material molar ratio:1.Isomerization reaction used catalyst is that 1.0%Mo and 3.0%MgO is modified jointly SAPO-5 molecular sieves；Isomerization reaction condition is：The mol ratio of ortho-xylene and meta-xylene is 1:1, reaction pressure is normal Pressure, reaction temperature are 250 DEG C, and gross mass air speed is 0.2 h-1；Using N2To react carrier gas, carrier gas and paraxylene and a diformazan Benzene total moles ratio is 3:1.Transalkylation reaction used catalyst is the sheet Beta molecules that 1.0%Ni and 5.0%CuO are modified jointly Sieve；Transalkylation reaction conditions are：The mol ratio of toluene and trimethylbenzene is 2:1, reaction pressure is 2.0 MPa, and reaction temperature is 430 DEG C, gross mass air speed is 0.2 h-1；Using H2Carrier gas is reacted, carrier gas is 1 with toluene and trimethylbenzene total moles ratio:2.I.e. Using cheap coal synthesis gas crude carbinol and coking crude benzene as raw material, by the above method, realize high selectivity, produce at low cost Paraxylene.Whole set process system overall reaction data are as follows：Benzene and methanol convert completely (benzene in the product after separation again Circulation is used as under reaction raw materials), the selectivity of paraxylene reaches 95.0% in aromatic product.Alkylation catalyst one way is run Life-span is up to 800 h（When methanol can not convert completely in alkylation reactor, it is believed that catalyst inactivation, following examples phase Together）.Wherein, the computational methods of Selectivity for paraxylene are as follows in aromatic product（Following examples are identical）：
Embodiment 2:
The present embodiment（Fig. 2）Difference from Example 1 is：1）Coal-based methanol raw material uses the made crude carbinol of coal tar furnace gas （The wt% of methanol content 93.0）；2）Process system introduces methylbenzene shape-selective disproportionation reaction device（Fixed bed）, i.e. toluene tower isolates Part toluene, into methylbenzene shape-selective disproportionation reaction device, reaction product is incorporated to alkylation reactor outlet together with unconverted toluene Material, together into rectification system；Shape-selective disproportionation reaction used catalyst is 0.01%Pd and 16.0%B2O3The ZSM- modified jointly 11 molecular sieves, reaction condition are：Reaction pressure is normal pressure, and reaction temperature is 700 DEG C, and gross mass air speed is 5.0 h-1；Using H2 To react carrier gas, carrier gas is 5 with material molar ratio:1.3）Alkylation reactor uses fixed bed reactors.4）Alkylated reaction Used catalyst is 0.02%Ce2O3The nano whiskers ZSM-5 molecular sieve composite modified with 0.1%MgO, external surface area 91 m2/ g, outer surface acidity bit quantity account for the 33% of total acidic bit quantity, and weak acid and middle strong acidity bit quantity account for total acidic bit quantity 96.5%；Alkylation reaction condition is：Methanol and aromatic hydrocarbons（Benzene+toluene）Mol ratio be 1:1, reaction pressure is 2.0 MPa, instead It is 480 DEG C to answer temperature, and water is 4 with material molar ratio:1, gross mass air speed is 10.0 h-1；Using H2To react carrier gas, carrier gas It is 10 with material molar ratio:1.Isomerization reaction used catalyst is 0.02%Pt and 10.0%Fe2O3The nanometer sheet modified jointly Shape ZSM-5 molecular sieve；Isomerization reaction condition is：The mol ratio of ortho-xylene and meta-xylene is 1:4, reaction pressure 2.0 MPa, reaction temperature are 500 DEG C, and gross mass air speed is 10.0 h-1；Using H2To react carrier gas, carrier gas is with material molar ratio 1:2.Transalkylation reaction used catalyst is the sheet MOR/ZSM-12 compound molecules that 5.0%Co and 1.0%ZnO are modified jointly Sieve；Transalkylation reaction conditions are：The mol ratio of toluene and trimethylbenzene is 1:4, reaction pressure is normal pressure, and reaction temperature is 350 DEG C, gross mass air speed is 10.0 h-1；Using N2To react carrier gas, carrier gas is 10 with material molar ratio:1.Other techniques are pacified Arrange same as Example 1.Whole set process system overall reaction data are as follows in the present embodiment：Benzene and methanol convert completely, aromatic hydrocarbons The selectivity of paraxylene reaches 93.3% in product.Alkylation catalyst single pass life is up to 2500 h.
Embodiment 3:
The present embodiment（Fig. 3）Difference from Example 1 is：1）Coal base benzene raw materials are using obtained by the lighting of coal tar heavy duty component Crude benzol, contain 79.8 wt% benzene, 15.0 wt% toluene, 5.0 wt% dimethylbenzene and 0.2 wt% other impurities；2）Alkylated reaction Device uses moving-burden bed reactor.3）Alkylated reaction used catalyst is 5.0%La2O3The composite modified sheet with 5.0%CaO MCM-49/ nanometer Beta composite molecular screens, external surface area are 102 m2/ g, outer surface acidity bit quantity account for total acidic bit quantity 37%, weak acid and middle strong acidity bit quantity account for the 95.8% of total acidic bit quantity；Alkylation reaction condition is：Methanol and aromatic hydrocarbons （Benzene and toluene）Mol ratio be 1:2, reaction pressure is 5.0 MPa, and reaction temperature is 700 DEG C, and water is with material molar ratio 10:1, gross mass air speed is 0.2 h-1；Using CO2To react carrier gas, carrier gas is 1 with material molar ratio:2.Isomerization reaction institute It is 5.0%Ni and 5.0% Ce with catalyst2O3The sheet MCM-56/ nanometer Beta composite molecular screens modified jointly；Isomerization reaction Condition is：The mol ratio of ortho-xylene and meta-xylene is 1:2, the MPa of reaction pressure 5.0, reaction temperature are 390 DEG C, always Mass space velocity is 6.0 h-1；Using H2To react carrier gas, carrier gas is 10 with material molar ratio:1.Transalkylation reaction is used to be catalyzed Agent is the SAPO-5 molecular sieves that 0.8%Fe and 10.0%CdO are modified jointly；Transalkylation reaction conditions are：Toluene and trimethylbenzene Mol ratio is 4:1, reaction pressure is 6.0 MPa, and reaction temperature is 700 DEG C, and gross mass air speed is 4.0 h-1；Using H2To be anti- Carrier gas is answered, carrier gas is 4 with material molar ratio:1.Other raw materials select and processing arrangement is same as Example 1.Whole set process system Overall reaction data are as follows：Benzene and methanol convert completely, and Selectivity for paraxylene reaches 97.0% in aromatic product.Alkylation is urged Agent single pass life is up to 1400 h.
Embodiment 4:
The present embodiment（Fig. 4）Difference from Example 2 is：1）Coal-based methanol raw material using the made crude carbinol of coal synthesis gas and The mixture of the made crude carbinol of oven gas（The wt% of methanol content 87.0）；2）Coal base crude benzol is coking benzene（Containing 98.79 wt% benzene, 1.0 wt% toluene, 0.2 wt% dimethylbenzene and 0.01 wt% other impurities）；3）Isomerization reaction and transalkylation reaction use N2As carrier gas;4) alkylated reaction used catalyst is the sheet MCM-56/ nanometers Beta that 2.5%CuO and 1.0%CaO is modified Composite molecular screen, external surface area are 92 m2/ g, outer surface acidity bit quantity account for the 32% of total acidic bit quantity, and weak acid is strong with Acid bit quantity accounts for the 96.9% of total acidic bit quantity；5）Shape-selective disproportionation reaction used catalyst is 2.0%Mo and 10.5%P2O5Altogether With the nano-sheet ZSM-5 molecular sieve of modification.Other processing arrangements and reaction condition are same as Example 2.Whole set process system Overall reaction data are as follows：Benzene and methanol convert completely, and the selectivity of paraxylene reaches 94.0% in aromatic product.Alkylation Catalyst single pass life is up to 2700 h.
Embodiment 5:
The present embodiment（Fig. 5）Difference from Example 2 is:1）Coal base benzene is split using coking benzene and coal tar heavy duty component hydrogenation The mixture of solution gained crude benzol（Containing 93.94 wt% benzene, 5.0 wt% toluene, 1.0 wt% dimethylbenzene and 0.06 wt%, other are miscellaneous Matter）.2）Coal-based methanol uses the made crude carbinol of coal synthesis gas（The wt% of methanol content 80.0）.3）Shape-selective disproportionation reaction is used to be catalyzed Agent is 5.0%Co and 5.0%SiO2The EU-1 molecular sieves modified jointly, shape-selective disproportionation reaction condition are：Reaction pressure is 5.0 MPa, reaction temperature are 300 DEG C, and gross mass air speed is 0.2 h-1；Using N2To react carrier gas, carrier gas is with material molar ratio 10:1.4）Alkylated reaction, isomerization reaction and transalkylation reaction use H2As carrier gas.5）Urged used in alkylated reaction Agent is the needle-like ZSM-5/ nanometer Beta composite molecular screens that 1.5%CuO and 2.0%MgO is modified, and external surface area is 99 m2/ g, Outer surface acidity bit quantity accounts for the 37% of total acidic bit quantity, and weak acid and middle strong acidity bit quantity account for total acidic bit quantity 97.4%.Isomerization reaction used catalyst is 5.0%Mo and 1.0%Fe2O3The SAPO-5/ nanometer Beta compound molecules modified jointly Sieve.Transalkylation reaction used catalyst is the MOR/ sheet Beta composite molecular screens that 0.01%Pt and 8.0%CuO are modified jointly. Other processing arrangements and reaction condition are same as Example 2.Whole set process system overall reaction data are as follows：Benzene and methanol are complete Convert, the selectivity of paraxylene reaches 93.5% in aromatic product.Alkylation catalyst single pass life is up to 3000 h.
Embodiment 6:
The present embodiment difference from Example 5 is:Methylbenzene shape-selective disproportionation reaction used catalyst is 1.0%Ni and 13.5% P2O5The SAPO-11 molecular sieves modified jointly；Shape-selective disproportionation reaction pressure is：2.0 MPa, reaction temperature are 460 DEG C, gross mass Air speed is 15.0 h-1；Using H2To react carrier gas, carrier gas is 1 with material molar ratio:2.Other processing arrangements, raw material selection and Reaction condition is same as Example 5.Whole set process system overall reaction data are as follows：Benzene and methanol convert completely, aromatic product The selectivity of middle paraxylene reaches 93.0%.Alkylation catalyst single pass life is up to 3000 h.
Comparative example
This comparative example shows that the new catalyst in traditional catalyst and the present invention is alkylated in petrobenzene and the simple step of methanol Catalytic performance in reaction, on the one hand it is intended to illustrate the high catalytic activity and diformazan of novel alkylation catalyst used in invention Benzene selectivity of product, on the other hand it is intended to illustrate the high product selectivity of invention methods described（Total bag）.Comparative example is alkylated Reaction is carried out in fixed bed reactors, traditional catalyst 1.0%La2O3With the compound traditional ZSM-5 modified jointly of 2.0%CaO （Cubic grain, 2 ~ 5 um, external surface area are 32 m2/ g, outer surface acidity bit quantity account for the 9.7% of total acidic bit quantity, Weak acid and middle strong acidity bit quantity account for the 73.1% of total acidic bit quantity）；Alkylation reaction condition is：The mol ratio of methanol and benzene For 1:1, reaction pressure is 2.0 MPa, and reaction temperature is 480 DEG C, and water is 4 with material molar ratio:1, gross mass air speed is 10.0 h-1；Using H2To react carrier gas, carrier gas is 10 with material molar ratio:1.Reaction result is as follows：Benzene conversion ratio is 42.1%, methanol conversion 100%, the selectivity of paraxylene is only 4.8% in aromatic product, and meta-xylene is selectively 9.6%, Ortho-xylene is selectively 4.7%, and methylbenzene selective 73.3%, other aromatic product contents are 7.6%, on the basis of phenyl ring Paraxylene yield is 2.0%, and the catalyst single pass life is 100 h.Under the same reaction conditions, in using the present invention Novel alkylation catalyst（The sheet MCM-56/ nanometer Beta composite molecular screens of 2.5%CuO and 1.0%CaO modifications）, simple one It is as follows to walk alkylated reaction result：Benzene conversion ratio is 68.6%, methanol conversion 100%, the selection of paraxylene in aromatic product Property be 7.5%, meta-xylene selectively be 15.1%, ortho-xylene selectively be 7.3%, methylbenzene selective 64.9%, other virtue Hydrocarbon products content is 5.2%, and the paraxylene yield on the basis of phenyl ring is 5.14%, and the alkylation catalyst single pass life reaches 2700 h.When using coal base crude benzol and coal base crude carbinol of the present invention for the method for raw material, with 2.5%CuO and 1.0% The sheet MCM-56/ nanometer Beta composite molecular screens of CaO modifications are alkylation catalyst, and benzene and methanol convert completely, aromatic hydrocarbons production The selectivity of paraxylene reaches 94.0% in thing（Embodiment 4）.

Claims (13)

  1. A kind of 1. method of coal-based feedstocks production paraxylene, it is characterised in that using coal base crude benzol and coal base crude carbinol as raw material, By pickling, weighted BMO spaces, alkylated reaction, rectifying, Crystallization Separation, isomerization reaction and transalkylation reaction, obtain pair Dimethylbenzene；Comprise the following steps that：
    （1）Coal base crude benzol is subjected to pickling and weighted BMO spaces, puts into together with coal base crude carbinol and/or successively and is alkylated instead Answer in device, while add the alkylation catalyst based on big external surface area, weak acid and middle strong acid and reaction carrier gas progress alkyl Change reaction；The mol ratio of coal base crude carbinol and coal base crude benzol is 1:1~1:6, reaction pressure is that normal pressure is warm to 5.0 MPa, reaction Spend for 350~700 DEG C, water is 1 with the mol ratio of coal base crude benzol and the total amount of coal base crude carbinol:2~10:1, gross mass air speed is 0.2~10.0 h-1；Carrier gas is 1 with the mol ratio of coal base crude benzol and the total amount of coal base crude carbinol:2~10:1；
    （2）Step（1）In alkylation reaction product and unreacted benzene enter distillation system, successively through stripping tower, benzene column and Toluene tower, for the lighter hydrocarbons isolated as device fuel, the benzene isolated and part toluene are recycled into alkylation reactor conduct Reaction raw materials, the heavy component of toluene tower outflow enter PX+MX（Paraxylene+meta-xylene）Rectifying column；PX+MX rectifying columns separate The paraxylene and meta-xylene mixture gone out enters isomerization reactor, while adds isomerization catalyst, to diformazan The mol ratio of benzene and meta-xylene is 1:1~1:4, reaction pressure is normal pressure to 5.0 MPa, and reaction temperature is 250~500 DEG C, Gross mass air speed is 0.1~10.0 h-1, using H2Or N2To react carrier gas, carrier gas and paraxylene and meta-xylene it is total Mol ratio is 1:2~10:1, reaction gained mixed xylenes is recycled into PX+MX rectifying columns；The weight of PX+MX rectifying columns outflow Component raw material enters ortho-xylene rectifying column, isolated ortho-xylene；The heavy constituent material of ortho-xylene rectifying column outflow enters Enter trimethylbenzene rectifying column, separating obtained trimethylbenzene enters transalkylation reactor, toluene with the separating obtained part toluene of toluene tower Mol ratio with trimethylbenzene is 1:4~4:1, reaction pressure is normal pressure to 6.0 MPa, and reaction temperature is 350~700 DEG C, always Mass space velocity is 0.1~10.0 h-1, using H2Or N2To react carrier gas, carrier gas is with the total moles of toluene and trimethylbenzene ratio 1:2~10:1；Products therefrom and unreacting material, which together circulate, is incorporated to step（1）In alkylation reaction product, into essence Evaporate system；The heavy component material of trimethylbenzene rectifying column outflow is as device liquid fuel.
  2. 2. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that step（1）In raw material Coal base crude carbinol is at least one of the made crude carbinol of coal tar furnace gas or the made crude carbinol of coal synthesis gas；In coal-based methanol raw material Methanol content is 80.0 ~ 93.0 wt%, and other impurities component is at least one in water, dimethyl ether, ethanol, butanol or amylalcohol etc. Kind.
  3. 3. the either method of coal-based feedstocks production paraxylene according to claim 1, it is characterised in that step（1）Raw material In coal base crude benzol be coking benzene, at least one of coal tar heavy duty component lighting crude benzol；In coal base crude benzol, in addition to benzene, also Containing 0.5 ~ 15.0 wt% toluene and a small amount of dimethylbenzene and other impurities, the other impurities are hexamethylene, nitrogenous or sulfur-bearing At least one of material.
  4. 4. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that step（1）Middle coal base is thick Benzoic acid is washed using sulfuric acid scrubbing method；The pretreatment of coal base crude benzole hydrogenation is carried out in fixed bed reactors, using NiO-MoO3And/or Co-MoO3Catalyst.
  5. 5. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that step（1）In alkane used Base catalyst uses sheet MCM-56, nano whiskers ZSM-5, sheet MCM-49 or the nanometer of two kinds of modified metal oxides Beta molecular sieves, or its compound；Two kinds of metal oxides are selected from La2O3、CaO、Ce2O3, MgO and CuO, metal in molecular sieve The content of oxide is 0.1 ~ 10.0 wt%.
  6. 6. the method for the coal-based feedstocks production paraxylene according to claim 1-5, it is characterised in that step（1）Middle institute State alkylation catalyst external surface area and be more than 90 m2/ g, outer surface acidity bit quantity account for the 30.0% of total acidic bit quantity with On, weak acid and middle strong acid quantity account for more than the 95% of total acidic bit quantity.
  7. 7. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that step（1）Middle alkylation Reaction carrier gas is H2Or CO2。
  8. 8. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that added in methods described Methylbenzene shape-selective disproportionation reaction, by step（2）Middle circulation is sent into shape-selective disproportionation reaction device, products therefrom as the toluene of reaction raw materials And unconverted toluene is together incorporated to step（1）In alkylation reaction product in, into distillation system.
  9. 9. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that step（1）Middle alkylation Reactor uses one kind in fixed bed reactors, fluidized-bed reactor or moving-burden bed reactor.
  10. 10. the either method of coal-based feedstocks production paraxylene according to claim 1, it is characterised in that isomerization, alkane Group-transfer and methylbenzene shape-selective disproportionation reaction device use fixed bed reactors.
  11. 11. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that isomerization reaction uses Catalyst is nano-sheet ZSM-5, sheet MCM-56, SAPO-5 or the nanometer Beta that metal is modified jointly with metal oxide Molecular sieve, or its compound；Metal is selected from Ni, Mo or Pt, and tenor is 0.01 ~ 5.0 wt% in the catalyst；Metal Oxide is selected from Ce2O3, MgO or Fe2O3, metal oxide content is 1.0 ~ 10.0 wt% in the catalyst.
  12. 12. the method for coal-based feedstocks production paraxylene according to claim 1, it is characterised in that step（2）Middle alkyl Transfer reaction using catalyst be sheet MOR, ZSM-12, sheet Bata that metal and transition metal oxide are modified jointly or SAPO-5 molecular sieves, or its compound；Metal promoter is selected from Fe, Co, Ni or Pt, in the catalyst tenor be 0.01 ~ 5.0 wt%；Transition metal oxide is selected from CuO, CdO or ZnO, in the catalyst transition metal oxide content be 1.0 ~ 10.0 wt%。
  13. 13. the method for coal-based feedstocks production paraxylene according to claim 8, it is characterised in that shape-selective disproportionation reaction makes It is nano-sheet ZSM-5, ZSM-11, SAPO-11 or EU-1 molecule that metal is modified jointly with nonmetal oxide with catalyst Sieve；Metal is selected from Pd, Mo, Co or Ni, and tenor is 0.01 ~ 5.0 wt% in the catalyst；Nonmetal oxide is selected from B2O3、P2O5Or SiO2, nonmetal oxide content is 5.0 ~ 16.0 wt% in the catalyst.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019125831A1 (en) * 2017-12-22 2019-06-27 Exxonmobil Chemical Patents Inc. Catalysts for producing paraxylene by methylation of benzene and/or toluene
CN110028983A (en) * 2019-04-26 2019-07-19 河南百优福生物能源有限公司 A kind of method that biomass pyrolysis liquid hydrogenation deoxidation oil prepares aromatic hydrocarbons
CN112661588A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Method and system for increasing yield of p-xylene
CN113045379A (en) * 2021-03-31 2021-06-29 江苏正丹化学工业股份有限公司 Method for co-producing mesitylene and durene by alkylation-isomerization of C8 or C9 aromatic hydrocarbon
CN114456035A (en) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 Aromatic hydrocarbon transalkylation method and system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103816935A (en) * 2014-02-27 2014-05-28 同济大学 Catalyst for selectively synthesizing p-xylene through alkylation reaction of coking benzene, toluene and methanol
CN106854135A (en) * 2015-12-09 2017-06-16 中国石油天然气股份有限公司 The method of benzene and methanol alkylation paraxylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103816935A (en) * 2014-02-27 2014-05-28 同济大学 Catalyst for selectively synthesizing p-xylene through alkylation reaction of coking benzene, toluene and methanol
CN106854135A (en) * 2015-12-09 2017-06-16 中国石油天然气股份有限公司 The method of benzene and methanol alkylation paraxylene

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019125831A1 (en) * 2017-12-22 2019-06-27 Exxonmobil Chemical Patents Inc. Catalysts for producing paraxylene by methylation of benzene and/or toluene
CN111511705A (en) * 2017-12-22 2020-08-07 埃克森美孚化学专利公司 Catalyst for producing p-xylene by methylation of benzene and/or toluene
JP2021506909A (en) * 2017-12-22 2021-02-22 エクソンモービル・ケミカル・パテンツ・インク Catalyst for the production of para-xylene by methylation of benzene and / or toluene
CN110028983A (en) * 2019-04-26 2019-07-19 河南百优福生物能源有限公司 A kind of method that biomass pyrolysis liquid hydrogenation deoxidation oil prepares aromatic hydrocarbons
CN112661588A (en) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 Method and system for increasing yield of p-xylene
CN114456035A (en) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 Aromatic hydrocarbon transalkylation method and system
CN113045379A (en) * 2021-03-31 2021-06-29 江苏正丹化学工业股份有限公司 Method for co-producing mesitylene and durene by alkylation-isomerization of C8 or C9 aromatic hydrocarbon
CN113045379B (en) * 2021-03-31 2023-09-22 江苏正丹化学工业股份有限公司 Method for co-producing mesitylene and durene by C8 aromatic hydrocarbon alkylation-isomerization

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