CN112694378B - Method for producing dimethylbenzene by taking oxygen-containing compound as raw material - Google Patents
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Abstract
The invention relates to a method for producing dimethylbenzene by taking an oxygen-containing compound as a raw material, which comprises the following steps: s1, after contacting and reacting a first oxygen-containing compound stream with an aromatization catalyst, separating to obtain a first C 1 + A non-aromatic hydrocarbon stream, a first C-containing 6 ‑C 7 An aromatic hydrocarbon stream, a first xylene-containing aromatic hydrocarbon stream, and a first C 8 + An aromatic hydrocarbon stream; s2, partial or whole first C 1 + The non-aromatic hydrocarbon material flow is separated to obtain a second C after the contact reaction with the aromatization catalyst 1 + A non-aromatic hydrocarbon stream, a second C-containing 6 ‑C 7 Aromatic hydrocarbon stream, second xylene-containing aromatic hydrocarbon stream, second C 8 + An aromatic hydrocarbon stream; s3, third C-containing 6 ‑C 7 The aromatic hydrocarbon stream is contacted with a methylation catalyst for reaction with a second oxygen-containing compound stream to obtain a third aromatic hydrocarbon stream containing dimethylbenzene; s4, the fourth C-containing material 6 ‑C 7 Aromatic hydrocarbon stream and third C 8 + And after the aromatic hydrocarbon stream is contacted with the transalkylation catalyst for reaction, obtaining a fourth aromatic hydrocarbon stream containing dimethylbenzene.
Description
Technical Field
The invention belongs to the technical field of aromatic hydrocarbon preparation, and particularly relates to a method for producing dimethylbenzene by taking an oxygen-containing compound as a raw material.
Background
Aromatic hydrocarbons (wherein benzene, toluene and xylene are respectively referred to as B, T and X, collectively referred to as BTX) are important basic organic chemical raw materials. About 90% of the aromatics worldwide originate from catalytic reforming processes and steam cracking by-product pyrolysis gasoline which use petroleum as a raw material, and the aromatics from coal routes account for only 10% of the total aromatics yield. As petroleum resources become depleted, the price is oscillated for a long time, which makes the energy chemical industry mainly comprising petroleum routes face unprecedented serious challenges.
The development of natural gas and shale gas in North America and the middle east produces a great deal of light hydrocarbon as byproduct. The light hydrocarbon of the shale gas byproduct replaces part of naphtha to be used as steam cracking, so that the steam cracking raw material has a light weight trend. In the future, there is a potential for a decrease in aromatics production from steam cracking byproducts, resulting in a trend toward shortage of aromatics production in the future worldwide. Therefore, the development of a new technology for producing aromatic hydrocarbon by taking oxygen-containing compounds including methanol as raw materials and partially replacing petroleum to produce aromatic hydrocarbon has great development potential.
U.S. patent No. 3931731 reports a process for preparing gasoline from methanol as a starting material. Although gasoline also contains a considerable amount of aromatic hydrocarbons, the process is mainly aimed at producing high-octane gasoline liquid fuel, and the product also contains a large amount of high-octane isoparaffin components. Therefore, the technology for preparing gasoline by taking the oxygen-containing compound as the raw material has the technical problem of low total aromatic hydrocarbon yield.
Chinese patent CN101671226 reports that a mixture of methanol and one or more of C1-C12 hydrocarbons is subjected to an aromatization reaction in an aromatization reactor. The method only considers one-time conversion of methanol and C1-C12 hydrocarbon, and does not relate to the process of circularly converting non-aromatic hydrocarbon in reaction products into aromatic hydrocarbon, so that the process has the problem of low aromatic hydrocarbon yield. Research shows that the reaction temperature of methane aromatization is as high as 700 ℃, but the conversion rate of methane is less than 20%, and the yield of aromatic hydrocarbon is only about 10%. The reaction temperature of aromatization in this process is only 650 ℃ at maximum. Thus, if the C1-C12 hydrocarbon component contains less reactive methane, the presence of methane or accumulation in the recycle stream may result in a decrease in the efficiency of the reactor.
Chinese patent CN101820919B reports a methanol or an oxygen-containing compoundA process for preparing a xylene product. In the process, B and T in the liquid aromatic hydrocarbon product are separated one by one, and meanwhile, non-aromatic hydrocarbon with carbon number more than C6 is also included. In the aromatic hydrocarbon mixture, the boiling points of non-aromatic hydrocarbons with the same carbon number and aromatic hydrocarbons are very close, and separation is difficult. In the existing aromatic hydrocarbon separation technology, generally, a mixed hydrocarbon stream containing benzene, toluene and xylene light aromatic hydrocarbon is subjected to solvent extraction to separate non-aromatic hydrocarbon from aromatic hydrocarbon, and then benzene, toluene, xylene and C are subjected to separation 9 + Aromatic hydrocarbons are separated one by one. In the process disclosed in chinese patent CN101820919B, non-aromatic hydrocarbons having a carbon number of not more than 6 are circularly converted into aromatic hydrocarbons, but non-aromatic hydrocarbons having a carbon number of not less than C6 are not circularly converted into aromatic hydrocarbons, and thus, the process has a problem of low aromatic hydrocarbon yield. The energy consumption of the separation process of liquid-phase aromatics from non-aromatics of chinese patent CN101820919B will be high compared to the direct use of the hydrocarbon mixture containing B, T.
Chinese patent CN101607864B reports a method for increasing xylenes yield by co-feeding benzene or toluene with oxygenates. The oxygenate to aromatics product contains a significant amount of non-aromatics, unconverted oxygenate and oxygenate intermediates in addition to the aromatics product. The non-aromatic hydrocarbon products have a plurality of components, are separately utilized or sold as a mixture, and have low added value. While benzene or toluene components in the reaction product or from the outside are added to the aromatization process, the xylene product may be upgraded by alkylation with methanol. However, since the methanol aromatization reaction product is very complex and the proper reaction conditions for methylation of benzene or toluene and methanol or dimethyl ether are not exactly the same, the efficiency of benzene or toluene reacting with methanol to produce xylene is inevitably affected when benzene or toluene is added into the methanol aromatization reactor.
An integrated device and a process method for preparing aromatic hydrocarbon by taking methanol as a raw material are disclosed in Chinese patent CN 103936541B: the methanol is subjected to an aromatization reactor to generate mixed hydrocarbon rich in aromatic hydrocarbon, and the mixed hydrocarbon is separated to obtain C1-2 hydrocarbon, C3-4 hydrocarbon, C5+ non-aromatic hydrocarbon, BTX and C9+ heavy aromatic hydrocarbon. Wherein, C1-C2 hydrocarbon, C5+ non-aromatic hydrocarbon and BTX are discharged as products, after C3-4 hydrocarbon is aromatized again, the products are directly mixed with C9+ heavy aromatic hydrocarbon as raw materials to enter a transalkylation reactor, the reaction products return to a separation tower, and a small amount of C9+ heavy aromatic hydrocarbon is discharged through a rectifying tower bottom pipeline.
Chinese patent 104045505A discloses a method and a device for preparing low-carbon aromatic hydrocarbon from methanol, wherein the methanol is subjected to aromatization reaction in an aromatization unit, reaction products enter a separator to be separated into low-carbon hydrocarbon gas products, oil phase products and water, the oil phase products are extracted in an aromatic hydrocarbon extraction unit, mixed aromatic hydrocarbon and raffinate oil are extracted, the raffinate oil and the low-carbon hydrocarbon gas of the methanol aromatization products enter a moving bed aromatization unit to be aromatized, gas products generated by the reaction are sent out of the device, and the oil phase products enter an aromatic hydrocarbon extraction unit, so that the defects of the prior art of aromatic hydrocarbon yield and selectivity are overcome, and the yield and selectivity of target product aromatic hydrocarbon are improved.
Chinese patent 105622306a provides a process for producing aromatic hydrocarbons from oxygenates as a feedstock, the process comprising: i) Reacting an oxygenate, preferably at least one of methanol and dimethyl ether, in at least one aromatization reactor to obtain an aromatization reaction product; passing said aromatization reaction product through a separation unit a, preferably comprising an operation unit such as quenching, caustic wash and/or water wash, to separate a gas phase hydrocarbon stream X and a liquid phase hydrocarbon stream Y; iii) Passing the gaseous hydrocarbon stream X through a separation unit B, preferably pressure swing adsorption, rectification and/or absorption, to remove gas and/or part of the oxygenates and to obtain a non-aromatic hydrocarbon-containing stream X1; or the gas-phase hydrocarbon stream X is subjected to separation unit B, preferably pressure swing adsorption, rectification and/or absorption, gas and/or partial oxygen-containing compounds are removed, and then the gas-phase hydrocarbon stream X is reacted in another aromatization reactor and is subjected to separation by a separation unit A, preferably an operation unit comprising quenching, alkaline washing, water washing and the like, so as to obtain a stream X2 containing non-aromatic hydrocarbon and a stream X3 containing aromatic hydrocarbon; combining the liquid-phase hydrocarbon stream Y and the optional aromatic hydrocarbon-containing stream X3, and separating by non-clear rectification of a separation unit C to obtain a mixed hydrocarbon stream M containing aromatic hydrocarbons with carbon number less than or equal to 7 and a residual hydrocarbon stream N; v) passing said remaining hydrocarbon stream N through a separation unit D, preferably comprising rectification and solvent extraction rectificationSeparating to obtain a non-aromatic hydrocarbon-containing stream K, a C8 aromatic hydrocarbon stream J and a C9+ aromatic hydrocarbon stream L; returning part or all of said non-aromatic hydrocarbon-containing stream X1 and non-aromatic hydrocarbon-containing stream X2, mixed hydrocarbon stream M containing less than or equal to 7 aromatic hydrocarbons in carbon number and/or non-aromatic hydrocarbon-containing stream K, optionally together with a further C2+ hydrocarbon stream, to the above oxygenates; or one of the non-aromatic hydrocarbon-containing stream X1 and the non-aromatic hydrocarbon-containing stream X2, the mixed hydrocarbon stream M containing less than or equal to 7 aromatic hydrocarbons and/or the non-aromatic hydrocarbon-containing stream K are partially or completely returned to the aromatization reactor in iii); optionally, the c9+ aromatic hydrocarbon stream L is reacted in at least one reactor selected from a transalkylation reactor and a dealkylation reactor to obtain a C8 aromatic hydrocarbon stream L1. The aromatic hydrocarbon of the product C6-C7 in the patent is directly used as a raw material without separation and enters an aromatization reactor together with an oxygen-containing compound to be contacted with a catalyst for conversion into C7 and C8 aromatic hydrocarbon. C6-C7 aromatic hydrocarbon as raw material enters an aromatization reactor, which tends to reduce the conversion rate of the oxygen-containing compound. And heavy aromatics C9 in the product + The dealkylation is carried out to convert into BTX, and low-value methane is a byproduct, so that the economic benefit of the process is reduced. C9C 9 + Heavy aromatics can also be converted to xylenes by disproportionation reaction with toluene. The system comprises a separation system of C6 and C7 aromatic hydrocarbon, and the separation of the C6-C7 aromatic hydrocarbon can generate larger energy consumption.
In summary, in the existing process of producing aromatic hydrocarbon by using oxygen-containing compounds as raw materials, the technical problems of high energy consumption and low added value of products exist.
Disclosure of Invention
Aiming at the technical problems of high energy consumption and low added value of products in the process of preparing the dimethylbenzene by taking the oxygen-containing compound as the raw material in the prior art, the invention provides a novel method for producing the dimethylbenzene by taking the oxygen-containing compound as the raw material, and the method has the advantages of low energy consumption and high added value of the products.
To this end, the present invention provides in a first aspect a process for producing xylenes starting from an oxygenate, comprising the steps of:
s1, contacting the first oxygen-containing compound stream with an aromatization catalyst in a first reactor to reactAfter that, a first C is obtained by separation 1 + A non-aromatic hydrocarbon stream, a first C-containing 6 -C 7 An aromatic hydrocarbon stream, a first xylene-containing aromatic hydrocarbon stream, and a first C 8 + An aromatic hydrocarbon stream;
s2, partial or whole first C 1 + The non-aromatic hydrocarbon material flow is contacted with aromatization catalyst in a second reactor for reaction, and then separated to obtain a second C 1 + A non-aromatic hydrocarbon stream, a second C-containing 6 -C 7 Aromatic hydrocarbon stream, second xylene-containing aromatic hydrocarbon stream, second C 8 + An aromatic hydrocarbon stream;
s3, third C-containing 6 -C 7 The aromatic hydrocarbon stream is contacted with a methylation catalyst for reaction with a second oxygen-containing compound stream to obtain a third aromatic hydrocarbon stream containing dimethylbenzene;
s4, the fourth C-containing material 6 -C 7 Aromatic hydrocarbon stream and third C 8 + And after the aromatic hydrocarbon stream is contacted with the transalkylation catalyst for reaction, obtaining a fourth aromatic hydrocarbon stream containing dimethylbenzene.
In the present invention, the reaction system for carrying out the above method comprises: an oxygenate reaction zone, a light hydrocarbon aromatization reaction zone, a methylation reaction zone, and a transalkylation reaction zone.
In some embodiments of the invention, the third C-containing 6 -C 7 The aromatic hydrocarbon stream is from a first C-containing stream 6 -C 7 Aromatic hydrocarbon stream and/or second C-containing stream 6 -C 7 An aromatic hydrocarbon stream.
In other embodiments of the present invention, the fourth C-containing component 6 -C 7 The aromatic hydrocarbon stream is from a first C-containing stream 6 -C 7 Aromatic hydrocarbon stream and/or second C-containing stream 6 -C 7 An aromatic hydrocarbon stream; the third C 8 + The aromatic hydrocarbon stream comes from the first C 8 + Aromatic hydrocarbon stream and/or second C 8 + An aromatic hydrocarbon stream.
In the present invention, from the first C-containing component 6 -C 7 The aromatic hydrocarbon may be all of the first C-containing 6 -C 7 The aromatic hydrocarbon stream, which may also be part of the first C-containing stream 6 -C 7 An aromatic hydrocarbon stream. From a second C-containing component 6 -C 7 The aromatic hydrocarbon stream may be all of the second C-containing 6 -C 7 Aromatic hydrocarbon stream, also part of the second C-containing stream 6 -C 7 An aromatic hydrocarbon stream. From the first C 8 + The aromatic hydrocarbon stream may be all of the first C 8 + Aromatic hydrocarbon stream, also part of the first C 8 + An aromatic hydrocarbon stream. From a second C 8 + The aromatic hydrocarbon stream may be all of the second C 8 + Aromatic hydrocarbon stream, also part of the second C 8 + An aromatic hydrocarbon stream.
In some embodiments of the invention, in step S1, the reaction conditions are: the reaction temperature is 360-550 ℃, the reaction pressure is 0.01-2.0 MPa, and the weight airspeed of the first oxygen-containing compound is 0.1-6.0 h -1 。
In other embodiments of the invention, in step S2, the reaction conditions are: the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-2.0 MPa, the first C 1 + The weight airspeed of the non-aromatic hydrocarbon is 0.1 to 6.0h -1 。
In some embodiments of the invention, the second C 1 + The non-aromatic hydrocarbon material flow returns to the second reactor to continue the reaction, thereby increasing the utilization rate of the raw materials.
In some embodiments of the invention, in step S3, the reaction conditions are: the reaction temperature is 350-540 ℃, the reaction pressure is 0.05-4.0 MPa, and the second oxygen-containing compound and C 6 -C 7 The molar ratio of the aromatic hydrocarbon is 2:1-1:4 and C 6 -C 7 The weight airspeed of the aromatic hydrocarbon is 0.5 to 4.0h -1 。
In other embodiments of the present invention, in step S4, the reaction conditions are: the reaction temperature is 300-540 ℃, the reaction pressure is 0.05-4.0 MPa, and the reaction pressure is C 6 -C 7 The weight space velocity of aromatic hydrocarbon is 0.6-4.0h -1 、C 6 -C 7 Aromatic hydrocarbons and C 8 + The molar ratio of the aromatic hydrocarbon is 2:1-1:3; preferably, the reaction is carried out under conditions comprising hydrogen, said hydrogen being reacted withThe molar ratio of aromatic hydrocarbon is 1:1-10:1, and the aromatic hydrocarbon is C 6 -C 7 Aromatic hydrocarbons and C 8 + Sum of aromatic hydrocarbons.
In the invention, in the steps S3 and S4, besides the aromatic hydrocarbon stream containing dimethylbenzene, byproduct non-aromatic hydrocarbon streams can be obtained, and the byproduct non-aromatic hydrocarbon streams can be returned to the second reactor for continuous reaction, so that the utilization rate of raw materials is increased.
In other embodiments of the present invention, in steps S1 and S2, the aromatization catalyst comprises at least one of ZSM-5 and ZSM-11 molecular sieves having a modifying component supported thereon; preferably, the modifying component is selected from at least one of Zn, ga, ag, mo, W, rare earth metal elements, mg, cu, mn, fe, co, ni, P, si, B, pt, pd, cl and oxides of the foregoing elements. In some embodiments of the invention, the active component is present in an amount of 1 to 3% by weight of the catalyst.
In some embodiments of the invention, in step S3, the methylation catalyst has a xylene shape selective function, and the selectivity of para-xylene in the product is greater than 70% in xylene.
In other embodiments of the invention, the first reactor and the second reactor are fluidized bed reactors or fixed bed reactors; preferably, the first reactor and the second reactor are fluidized bed reactors.
In some embodiments of the invention, the first and second oxygenates are at least one of an alcohol compound and an ether compound; preferably, the alcohol compound is methanol, and the ether compound is dimethyl ether.
In some embodiments of the invention, the method specifically comprises the following steps, which are specifically shown in fig. 1:
(1) Contacting the first oxygenate stream 1 with an aromatization catalyst in a first reactor in an oxygenate aromatization reaction zone R101 to react, and separating to obtain a first C 1 + Non-aromatic hydrocarbon stream 2, first C-containing 6 -C 7 Aromatic hydrocarbonsStream 3, first xylene-containing aromatic hydrocarbon stream 4 and first C 8 + Aromatic hydrocarbon stream 5;
(2) Part or all of the first C 1 + The non-aromatic hydrocarbon material flow 2 is contacted with an aromatization catalyst in a second reactor in a light hydrocarbon aromatization reaction zone R102 for reaction, and then separated to obtain a second C 1 + Non-aromatic hydrocarbon stream 6, second C-containing 6 -C 7 Aromatic hydrocarbon stream 7, second xylene-containing aromatic hydrocarbon stream 8, second C 8 + Aromatic hydrocarbon stream 9; optionally, the second C 1 + The non-aromatic hydrocarbon stream 6 is returned to the second reactor to continue to participate in the reaction;
(3) Third C-containing 6 -C 7 After contacting the aromatic hydrocarbon stream 10 with a second oxygenate stream 11 in a methylation reaction zone R103 with a methylation catalyst, a third xylene-containing aromatic hydrocarbon stream 12 is obtained; wherein the third C-containing 6 -C 7 Aromatic hydrocarbon stream 10 is from a first C-containing stream 6 -C 7 Aromatic hydrocarbon stream 3 and/or second C-containing 6 -C 7 Aromatic hydrocarbon stream 7;
(4) Fourth C-containing 6 -C 7 Aromatic hydrocarbon stream 13 and third C 8 + After contacting the aromatic hydrocarbon stream 14 with a transalkylation catalyst in transalkylation reaction zone R404, a fourth xylene-containing aromatic hydrocarbon stream 15 is obtained; wherein the fourth C-containing component 6 -C 7 Aromatic hydrocarbon stream 13 is from a first C-containing stream 6 -C 7 Aromatic hydrocarbon stream 3 and/or second C-containing 6 -C 7 Aromatic hydrocarbon stream 7, the third C 8 + Aromatic hydrocarbon stream 14 is from a first C 8 + Aromatic hydrocarbon stream 5 and/or second C 8 + Aromatic hydrocarbon stream 9.
The beneficial effects of the invention are as follows: the method takes the oxygen-containing compound as the raw material, C in the aromatization product 6 -C 7 The aromatic hydrocarbon of the method is directly used as a raw material for methylation and transalkylation without separation, so that the method has the advantages of low energy consumption and high added value of products, and can be used in the production of dimethylbenzene.
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The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present invention may be prepared by commercial or conventional methods unless specifically indicated.
Example 1
1) At 400℃and methanol weight space velocity of 0.5h -1 Under the condition of the reaction pressure of 0.1MPa, the methanol material flow 1 is contacted with an aromatization catalyst in an oxygen-containing compound reaction zone R101 fluidized bed reactor for reaction, and then separated to obtain a first C 1 + Non-aromatic hydrocarbon stream 2, first C-containing 6 -C 7 Aromatic hydrocarbon stream 3, first xylene-containing aromatic hydrocarbon stream 4, first C 8 + Aromatic hydrocarbon stream 5. Wherein the aromatization catalyst is: 3.0% Ag/ZSM-5.
2) At a reaction temperature of 550 ℃, a first C 1 + Weight space velocity of non-aromatic hydrocarbon 1.0h -1 Under the condition of 0.2MPa of reaction pressure, all the first C 1 + The non-aromatic hydrocarbon material flow 2 is contacted with an aromatization catalyst in a light hydrocarbon aromatization reaction zone R202 fluidized bed reactor for reaction, and then separated to obtain a second C 1 + Non-aromatic hydrocarbon stream 6, second C-containing 6 -C 7 Aromatic hydrocarbon stream 7, second xylene-containing aromatic hydrocarbon stream 8, second C 8 + Aromatic hydrocarbon stream 9. Wherein the aromatization catalyst is: 3.0% Ga/ZSM-5.
3) At 420 ℃, methanol and C 6 -C 7 Aromatic hydrocarbon molar ratio is 1:1, C 6 -C 7 Weight space velocity of aromatic hydrocarbon 2.0h -1 Under the condition of 0.5MPa of reaction pressure, the third C-containing material 6 -C 7 The aromatic hydrocarbon stream 10 is reacted with a methanol stream 11 in a methylation reaction zone R303 in contact with a methylation catalyst to produce a third xylene-containing aromatic hydrocarbon stream 12, wherein stream 10 is derived from 50% by weight of stream 3 and 50% by weight of the productStream 7. Methylation catalyst employed 2.0% P 2 O 5 /ZSM-5。
4) At 420 ℃, the reaction pressure is 1.0MPa, C 6 -C 7 Weight space velocity of aromatic hydrocarbon 2.0h -1 、C 6 -C 7 Aromatic hydrocarbons and C 8 + The fourth C-containing component under the conditions that the aromatic hydrocarbon molar ratio is 1:1 and the hydrogen and aromatic hydrocarbon molar ratio is 2:1 6 -C 7 Aromatic hydrocarbon stream 13 and third C 8 + Aromatic hydrocarbon stream 14 is reacted in contact with a transalkylation catalyst in transalkylation reaction zone R404 to produce a fourth xylene-containing aromatic hydrocarbon stream 15, wherein stream 14 is from all of stream 5 and all of stream 9, and stream 13 is from 50 weight percent of stream 3 and 50 weight percent of stream 7. The transalkylation catalyst used was 2% Mo/ZSM-12.
The yield of xylenes in the product was 78.2% based on the feed of methanol (hydro-carbon group) to the oxygenate reaction zone R101.
Example 2
1) At 540℃and methanol weight space velocity of 4.0h -1 Under the condition of the reaction pressure of 1.0MPa, the methanol material flow 1 is contacted with an aromatization catalyst in an oxygen-containing compound reaction zone R101 fluidized bed reactor for reaction, and then separated to obtain a first C 1 + Non-aromatic hydrocarbon stream 2, first C-containing 6 -C 7 Aromatic hydrocarbon stream 3, first xylene-containing aromatic hydrocarbon stream 4, first C 8 + Aromatic hydrocarbon stream 5. The aromatization catalyst is as follows: 1.5% Ag+1.5% Co/ZSM-5.
2) At a reaction temperature of 550 ℃, a first C 1 + Weight space velocity of non-aromatic hydrocarbon 4.0h -1 Under the condition of reaction pressure of 1.0MPa, all the first C 1 + The non-aromatic hydrocarbon material flow 2 is contacted with an aromatization catalyst in a light hydrocarbon aromatization reaction zone R202 fluidized bed reactor for reaction, and then separated to obtain a second C 1 + Non-aromatic hydrocarbon stream 6, second C-containing 6 -C 7 Aromatic hydrocarbon stream 7, second xylene-containing aromatic hydrocarbon stream 8, second C 8 + Aromatic hydrocarbon stream 9. The aromatization catalyst is as follows: 3.0% Ga/ZSM-5.
3) Methanol and C at 400 DEG C 6 -C 7 Aromatic hydrocarbon molar ratio of 2:1, C 6 -C 7 Weight space velocity of aromatic hydrocarbon 4.0h -1 Under the condition of 2.0MPa of reaction pressure, the third C-containing material 6 -C 7 The aromatic hydrocarbon stream 10 is reacted with a methanol stream 11 in a methylation reaction zone R303 in contact with a methylation catalyst to produce a third xylene-containing aromatic hydrocarbon stream 12, wherein stream 10 is derived from 50% by weight of stream 3 and 50% by weight of stream 7. The methylation catalyst adopts 2.0% P 2 O 5 /ZSM-5。
4) At 500 ℃, C 6 -C 7 Weight space velocity of aromatic hydrocarbon 4.0h -1 、C 6 -C 7 Aromatic hydrocarbons and C 8 + The fourth C-containing reaction under the conditions that the aromatic hydrocarbon molar ratio is 1:1 and the molar ratio of hydrogen to aromatic hydrocarbon stream is 4:1 and the reaction pressure is 0.1MPa 6 ～C 7 Aromatic hydrocarbon stream 13 and third C 8 + Aromatic hydrocarbon stream 14 is reacted in contact with a transalkylation catalyst in transalkylation reaction zone R404 to produce a fourth xylene-containing aromatic hydrocarbon stream 15, wherein stream 14 is from all of stream 5 and all of stream 9, and stream 13 is from 50 weight percent of stream 3 and 50 weight percent of stream 7. The transalkylation catalyst used was 2% Mo/ZSM-12.
The yield of xylenes in the product was 72.6% based on the feed of methanol (hydro-carbon) to the oxygenate reaction zone R101.
Example 3
1) At 480℃and methanol weight space velocity of 1.5h -1 Under the condition of the reaction pressure of 2.0MPa, the methanol material flow 1 is contacted with an aromatization catalyst in an oxygen-containing compound reaction zone R101 fluidized bed reactor for reaction, and then separated to obtain a first C 1 + Non-aromatic hydrocarbon stream 2, first C-containing 6 -C 7 Aromatic hydrocarbon stream 3, first xylene-containing aromatic hydrocarbon stream 4, first C 8 + Aromatic hydrocarbon stream 5. The aromatization catalyst is as follows: 3.0% Ag/ZSM-12.
2) At a reaction temperature of 560 ℃ and a first C 1 + Weight space velocity of non-aromatic hydrocarbon 2.0h -1 Under the condition of 2.0MPa of reaction pressure, all the first C 1 + Non-aromatic hydrocarbon stream 2 is in light hydrocarbon aromatization reaction zone R202 the second C is obtained by separation after the contact reaction with the aromatization catalyst in the fluidized bed reactor 1 + Non-aromatic hydrocarbon stream 6, second C-containing 6 -C 7 Aromatic hydrocarbon stream 7, second xylene-containing to obtain aromatic hydrocarbon stream 8, second C 8 + Aromatic hydrocarbon stream 9. The aromatization catalyst is as follows: 3.0% Ga/ZSM-5.
3) At 420 ℃, dimethyl ether and C 6 -C 7 The molar ratio of the aromatic hydrocarbon is 1:1.5 and C 6 -C 7 Weight space velocity of aromatic hydrocarbon 2.0h -1 Under the condition of 0.5MPa of reaction pressure, the third C-containing material 6 -C 7 The aromatic hydrocarbon stream 10 is reacted with a dimethyl ether stream 11 in a methylation reaction zone R303 in contact with a methylation catalyst to produce a third xylene-containing aromatic hydrocarbon stream 12, wherein stream 10 is derived from stream 3 having a weight fraction of 70% and stream 7 having a weight fraction of 70%. The methylation catalyst adopts 2.0% P 2 O 5 /ZSM-5。
4) At 420 ℃ C 6 -C 7 Weight space velocity of aromatic hydrocarbon 2.0h -1 、C 8 + Weight space velocity of aromatic hydrocarbon 1.5h -1 、C 6 -C 7 Aromatic hydrocarbons and C 8 + The molar ratio of the aromatic hydrocarbon is 1:2, the molar ratio of the hydrogen to the aromatic hydrocarbon stream is 10:1, and the fourth C-containing material is under the condition of the reaction pressure of 4.0MPa 6 -C 7 Aromatic hydrocarbon stream 13 and third C 8 + Aromatic hydrocarbon stream 14 is reacted in contact with a transalkylation catalyst in transalkylation reaction zone R404 to produce a fourth xylene-containing aromatic hydrocarbon stream 15, wherein stream 14 is derived from all stream 5 and all stream 9, and stream 13 is derived from 30 weight percent stream 3 and 30 weight percent stream 7. The transalkylation catalyst used was 2% Mo/ZSM-12.
The yield of xylenes in the product was 79.5% based on the feed of methanol (hydro-carbon) to the oxygenate reaction zone R101.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (9)
1. A process for producing xylenes from an oxygenate feedstock comprising the steps of:
s1, separating a first oxygen-containing compound stream after contact reaction with an aromatization catalyst in a first reactor to obtain a first C 1 + A non-aromatic hydrocarbon stream, a first C-containing 6 -C 7 An aromatic hydrocarbon stream, a first xylene-containing aromatic hydrocarbon stream, and a first C 8 + An aromatic hydrocarbon stream;
s2, partial or whole first C 1 + The non-aromatic hydrocarbon material flow is contacted with aromatization catalyst in a second reactor for reaction, and then separated to obtain a second C 1 + A non-aromatic hydrocarbon stream, a second C-containing 6 -C 7 Aromatic hydrocarbon stream, second xylene-containing aromatic hydrocarbon stream, second C 8 + An aromatic hydrocarbon stream;
s3, third C-containing 6 -C 7 The aromatic hydrocarbon stream is contacted with a methylation catalyst for reaction with a second oxygen-containing compound stream to obtain a third aromatic hydrocarbon stream containing dimethylbenzene;
s4, the fourth C-containing material 6 -C 7 Aromatic hydrocarbon stream and third C 8 + And after the aromatic hydrocarbon stream is contacted with the transalkylation catalyst for reaction, obtaining a fourth aromatic hydrocarbon stream containing dimethylbenzene.
2. The method of claim 1, wherein the third C-containing 6 -C 7 The aromatic hydrocarbon stream is from a first C-containing stream 6 -C 7 Aromatic hydrocarbon stream and/or second C-containing stream 6 -C 7 An aromatic hydrocarbon stream;
and/or the fourth C-containing 6 -C 7 The aromatic hydrocarbon stream is from a first C-containing stream 6 -C 7 Aromatic hydrocarbon stream and/or second C-containing stream 6 -C 7 An aromatic hydrocarbon stream; the third C 8 + The aromatic hydrocarbon stream comes from the first C 8 + Aromatic hydrocarbon stream and/or second C 8 + An aromatic hydrocarbon stream.
3. The method according to claim 1, wherein in step S1, the reaction conditions are: the reaction temperature is 360-550 ℃, the reaction pressure is 0.01-2.0 MPa, and the weight airspeed of the first oxygen-containing compound is 0.1-6.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or, in step S2, the reaction conditions are: the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-2.0 MPa, the first C 1 + The weight airspeed of the non-aromatic hydrocarbon is 0.1 to 6.0h -1 ；
And/or, in step S3, the reaction conditions are: the reaction temperature is 350-540 ℃, the reaction pressure is 0.05-4.0 MPa, and the second oxygen-containing compound and C 6 -C 7 The molar ratio of the aromatic hydrocarbon is 2:1-1:4 and C 6 -C 7 The weight airspeed of the aromatic hydrocarbon is 0.5 to 4.0h -1 ；
And/or, in step S4, the reaction conditions are: the reaction temperature is 300-540 ℃, the reaction pressure is 0.05-4.0 MPa, and the reaction pressure is C 6 -C 7 The weight space velocity of aromatic hydrocarbon is 0.6-4.0h -1 、C 6 -C 7 Aromatic hydrocarbons and C 8 + The molar ratio of the aromatic hydrocarbon is 2:1-1:3.
4. A process according to claim 3, wherein in step S4 the reaction is carried out under hydrogen-containing conditions, the molar ratio of hydrogen to aromatic hydrocarbon being from 1:1 to 10:1, the aromatic hydrocarbon being C 6 -C 7 Aromatic hydrocarbons and C 8 + Sum of aromatic hydrocarbons.
5. The process of any one of claims 1-4, wherein the aromatization catalyst, methylation catalyst, and transalkylation catalyst comprise at least one of ZSM-5 and ZSM-11 molecular sieves having a modifying component supported thereon;
and/or the first oxygen-containing compound and the second oxygen-containing compound are at least one of alcohol compounds and ether compounds.
6. The method of claim 5, wherein the modifying component is selected from the group consisting of Zn, ga, ag, mo, W, rare earth elements, mg, cu, mn, fe, co, ni, P, si, B, pt, pd, cl, and oxides of the foregoing.
7. The method of claim 5, wherein the alcohol compound is methanol and the ether compound is dimethyl ether.
8. The process of any one of claims 1-4 or 6 or 7, wherein the first and second reactors are fluidized bed reactors or fixed bed reactors.
9. The method of claim 5, wherein the first reactor and the second reactor are fluidized bed reactors or fixed bed reactors.
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| CN101823929A (en) * | 2010-04-14 | 2010-09-08 | 清华大学 | System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether |
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| EP3153489A1 (en) * | 2014-06-04 | 2017-04-12 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Method for preparing paraxylene and propylene by methanol and/or dimethyl ether |
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| CN101823929A (en) * | 2010-04-14 | 2010-09-08 | 清华大学 | System and process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether |
| CN104892346A (en) * | 2014-03-07 | 2015-09-09 | 中石化洛阳工程有限公司 | Method and apparatus for preparing p-xylene from methanol |
| EP3153489A1 (en) * | 2014-06-04 | 2017-04-12 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Method for preparing paraxylene and propylene by methanol and/or dimethyl ether |
| CN106608783A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for preparing xylene from methanol |
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