CN108017485B - Process for preparing aromatic hydrocarbon and combustible gas from methanol - Google Patents
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 116
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 87
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 86
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 77
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 111
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000008096 xylene Substances 0.000 claims description 45
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 19
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 239000012071 phase Substances 0.000 description 31
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 23
- 150000002431 hydrogen Chemical class 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000010791 quenching Methods 0.000 description 7
- 238000007323 disproportionation reaction Methods 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 methyl aromatic hydrocarbon Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- FHYUCVWDMABHHH-UHFFFAOYSA-N toluene;1,2-xylene Chemical group CC1=CC=CC=C1.CC1=CC=CC=C1C FHYUCVWDMABHHH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a process method for preparing aromatic hydrocarbon and combustible gas by using methanol, which mainly solves the problems of large investment and poor technical economy in the prior art. The invention adopts the following steps: 1) methanol is converted into a methanol aromatization product through a methanol-to-aromatics unit; 2) the methanol aromatization product is separated into a gas phase, an oil phase and a water phase in a first separation unit; 3) separating the oil phase into a non-aromatic stream and a first aromatic stream by a second separation unit; 4) the non-aromatic material flow and the gas phase are sent to a third separation unit to be separated into combustible gas, light hydrocarbon flow and second aromatic material flow; 5) the light hydrocarbon material flow is converted into a light hydrocarbon aromatization product through a light hydrocarbon aromatization unit; 6) the light hydrocarbon aromatization product returns to the third separation unit; 7) the technical scheme that the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are sent to the aromatic hydrocarbon combination device to be processed better solves the problems, and can be used in the industrial production of preparing aromatic hydrocarbon from methanol.
Description
Technical Field
The invention relates to a process method for preparing aromatic hydrocarbon and combustible gas by using methanol.
Technical Field
Aromatic hydrocarbons, in particular the light aromatic hydrocarbons BTX (benzene, toluene, xylene), are important basic organic chemicals, second only to ethylene and propylene in terms of yield and scale. Among the aromatic hydrocarbons, para-xylene is a product with high added value. Para-xylene is an important feedstock for the polyester industry, primarily for the production of Purified Terephthalic Acid (PTA) or purified dimethyl terephthalate (DMT), from which Polyester (PET) is produced.
Light aromatics are usually produced by a catalytic reforming and aromatics complex using naphtha as a feedstock. The preparation of the aromatic hydrocarbon by the methanol is a new technical route for preparing the aromatic hydrocarbon by taking coal-based methanol as a raw material. China is rich in coal resources, and the development of a methanol-to-aromatic technology is an important supplement for the preparation of aromatic hydrocarbons by the traditional petrochemical route.
The technology for preparing aromatic hydrocarbon from methanol is a process for producing aromatic hydrocarbon by the steps of dehydrogenation, cyclization and the like under the catalytic action of a bifunctional (acidic and dehydrogenation) active catalyst by taking methanol as a raw material. In the aromatization process, aromatic hydrocarbons such as benzene, toluene and xylene are generated, and by-products comprise hydrocarbons such as methane, ethylene and propylene and hydrogen. Due to the complexity of the reaction product, a complicated separation procedure is required to obtain the final xylene product.
CN101671226 discloses a process for preparing xylene by methanol aromatization. The mixture of methanol and one or more of C-C in the methanol aromatization reactor is subjected to aromatization reaction to produce hydrogen, low-carbon hydrocarbons, xylene and liquid-phase hydrocarbons other than xylene.
CN101823929 discloses a system and a process for preparing aromatic hydrocarbon by converting methanol or dimethyl ether, belonging to the technical field of aromatic hydrocarbon production. The raw material methanol or dimethyl ether is firstly reacted in an aromatization reactor, after the reaction products are separated, H2, methane, mixed C8 aromatic hydrocarbons and part of C9+ hydrocarbons are used as a product output system, and C2+ non-aromatic hydrocarbons and aromatic hydrocarbons except the mixed C8 aromatic hydrocarbons and part of C9+ hydrocarbons are used as circulating material flows and returned to the corresponding reactor for further aromatization reaction.
CN103755514 discloses a system for preparing benzene and xylene by alcohol ether conversion. The system comprises a methanol/dimethyl ether aromatization reaction system, a gas-liquid three-phase separation device, a benzene fractionation device, a benzene extraction system, a xylene fractionation system, a de-olefin device, a methyl aromatic hydrocarbon disproportionation device, a disproportionation product separation device, a paraxylene separation device, a xylene isomerization device, an isomerization product separation device, a paraxylene product tower and a gas phase separation system. The invention also provides a method for preparing benzene and p-xylene based on the system, wherein toluene and C are used for preparing the benzene and the p-xylene9The utilization technology of heavy aromatics improves the yield of target products and simultaneously makes full use of gas phase C in primary reactants of aromatization of methanol and dimethyl ether2+ hydrocarbons as feedstock for a methanol/dimethyl ether aromatization system; hydrogen by-product for toluene and C9、C10Disproportionation of methyl aromatics and C8Isomerization reaction of aromatic hydrocarbon.
CN103864565 discloses a system and a method for preparing p-xylene by alcohol/ether conversion. The system mainly comprises an alcohol/ether aromatization reaction device, a gas-liquid three-phase separation device, a benzene fractionation device, a xylene fractionation device, an olefin removal device, a paraxylene separation device and a paraxylene finished product tower; wherein the yield of the p-xylene is improved by utilizing aromatization reaction of non-aromatic hydrocarbon, alkylation reaction of benzene and disproportionation reaction of toluene and aromatic hydrocarbon above C9; meanwhile, the non-clear separation technology of products below C7 is adopted, an aromatic extraction system is omitted, the investment and the energy consumption are greatly reduced, and the hydrocarbons above gas phase C2 are fully utilized as the raw materials of an alcohol/ether aromatization system; the hydrogen produced was used for the disproportionation of toluene and C9 methyl aromatics, C10 methyl aromatics and isomerization of C8 aromatics.
The invention disclosed above considers the characteristics of the reaction product of preparing aromatic hydrocarbon from methanol, develops a reaction product separation system and an aromatic hydrocarbon conversion system in a targeted manner, reduces the operation cost by utilizing the by-product hydrogen, reduces the equipment investment by omitting an aromatic hydrocarbon extraction system, and improves the technical economy of the device for preparing aromatic hydrocarbon from methanol to a certain extent. The large investment in aromatics conversion and separation units is well known. The existing aromatics complex is used for separating and converting the reaction product of preparing the aromatics from the methanol, so that the equipment and engineering investment can be further reduced, and the technical economy of the technology for preparing the aromatics from the methanol is improved. However, the untreated reaction product of methanol to aromatics is not suitable for being directly sent to the existing aromatics complex for subsequent treatment. This is because existing aromatics complexes are specifically designed for the subsequent separation and conversion of naphtha catalytic reformate. The BTX content in the reformed oil is generally 40-70% (mass fraction), wherein benzene is 8-12%, toluene is 16-28%, and xylene is 16-30%. For example, a typical ratio of benzene, toluene, and xylene in the reformate is 1:2: 2.4. And the aromatic hydrocarbon in the reaction product of preparing the aromatic hydrocarbon by the methanol is about 50 percent (mass fraction), wherein the content of benzene is less than 5 percent, and the content of xylene is more than 60 percent. A typical benzene to toluene xylene ratio is 1:7: 36. Therefore, the aromatic hydrocarbon product in the prior art cannot be directly sent to the prior aromatic hydrocarbon integrated unit for subsequent treatment.
Therefore, the problems of large investment and poor technical economy still exist in the prior art, and the invention aims to solve the problems.
Disclosure of Invention
The invention aims to solve the technical problems that the investment is large, the technical economy is poor and the aromatic hydrocarbon product in the prior art can not be directly sent to the prior aromatic hydrocarbon combination device for subsequent treatment in the prior art, and provides a novel process method for preparing aromatic hydrocarbon and combustible gas from methanol. The device has the advantages of fully utilizing the existing aromatic hydrocarbon combination device, reducing equipment investment, improving the overall technical competitiveness of projects, and directly sending aromatic hydrocarbon products obtained by reaction into the existing aromatic hydrocarbon combination device for subsequent treatment.
In order to solve the problems, the technical scheme adopted by the invention is as follows: a process method for preparing aromatic hydrocarbon and combustible gas by methanol comprises the following steps: 1) methanol is converted into a methanol aromatization product through a methanol-to-aromatics unit; 2) the methanol aromatization product is separated into a gas phase, an oil phase and a water phase in a first separation unit; 3) separating the oil phase into a non-aromatic stream and a first aromatic stream by a second separation unit; 4) the non-aromatic material flow and the gas phase are sent to a third separation unit to be separated into combustible gas, light hydrocarbon flow and second aromatic material flow; 5) the light hydrocarbon material flow is converted into a light hydrocarbon aromatization product through a light hydrocarbon aromatization unit; 6) the light hydrocarbon aromatization product is returned to the third separation unit.
In the above technical scheme, preferably, the first aromatic hydrocarbon stream and the second aromatic hydrocarbon stream are sent to an aromatic hydrocarbon combination unit for treatment.
In the above technical scheme, preferably, the first aromatic hydrocarbon stream and the second aromatic hydrocarbon stream are directly sent to the aromatic hydrocarbon combination unit for treatment.
In the above technical scheme, the methanol aromatization reaction conditions are as follows: the reaction temperature is 450-600 ℃, the reaction pressure is 0.1-0.5 MPA, and the reaction mass airspeed is 0.5-4 HR-1。
In the above technical scheme, the light hydrocarbon aromatization reaction conditions are as follows: the reaction temperature is 500-650 ℃, the reaction pressure is 0.1-1 MPA, and the reaction mass airspeed is 0.1-3 HR-1。
In the technical scheme, the optimal light hydrocarbon aromatization reaction temperature is 520-580 ℃;
in the technical scheme, the preferable light hydrocarbon aromatization reaction temperature is 540-560 ℃.
In the above technical scheme, the benzene content in the first aromatic hydrocarbon stream is not more than 5% (by mass fraction).
In the above technical solution, the xylene content in the first aromatic hydrocarbon stream is greater than 50% (by mass fraction), and preferably, the xylene content in the first aromatic hydrocarbon stream is greater than 60% (by mass fraction).
In the above technical scheme, the xylene content in the second aromatic hydrocarbon stream is not more than 25% (by mass fraction).
In the above technical scheme, the benzene and toluene content in the second aromatic hydrocarbon stream is greater than 40% (by mass fraction). Preferably, the second aromatic hydrocarbon stream has a benzene and toluene content of greater than 50% (by mass fraction).
In the technical scheme, the total weight content of hydrogen, methane and ethane in the light hydrocarbon material flow is less than 1%. Preferably, the total weight content of hydrogen, methane and ethane in the light hydrocarbon stream is less than 0.1%. In the above technical solution, the combustible gas comprises hydrogen, methane and ethane.
By adopting the method, the methanol is converted into light hydrocarbons such as hydrogen, methane, ethylene, ethane and the like and aromatic hydrocarbons such as benzene, toluene, xylene and the like in the methanol aromatization reactor, and simultaneously a large amount of water is produced as a byproduct. After cooling by non-contact cooling (e.g., heat exchanger) and contact cooling (quench tower), the reaction product separates into a gas phase, an oil phase, and water. Wherein the oil phase is mainly aromatic hydrocarbons and also contains a small amount of non-aromatic hydrocarbons. The separated non-aromatic hydrocarbon and the light hydrocarbon in the gas phase are sent to a light hydrocarbon aromatization unit.
By adopting the method, the aromatic hydrocarbon yield is further improved by the light hydrocarbon material flow through aromatization reaction, and more benzene and toluene are obtained at the same time, so that the benzene content and the toluene content in the material flow after the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are converged are increased, and the total content of xylene is reduced, so that the aromatic hydrocarbon material flow sent into the aromatic hydrocarbon combination device for treatment is closer to the material composition of catalytic reforming oil. However, due to the high selectivity of the methanol to aromatics reaction to mixed xylenes, the combined stream still contains a higher amount of xylenes in BTX (typically greater than 50%) than the reformate xylenes from conventional catalytic petroleum reforming (a typical value of 44%). Therefore, under the condition of insufficient operation flexibility, the xylene column and the paraxylene adsorption separation unit or crystallization separation unit of the aromatic hydrocarbon device need to be subjected to capacity expansion modification. In addition, due to the high selectivity of the methanol-to-aromatics catalyst to PX (generally, PX accounts for more than 50% of the xylene in the liquid-phase methanol-to-aromatics product), the amount of the feed entering the isomerization unit after adsorption separation of paraxylene does not change significantly, so that the isomerization unit, the disproportionation unit, the aromatics extraction unit and other units can adapt to the feed from the methanol-to-aromatics system.
By adopting the method, the device for preparing aromatic hydrocarbon from methanol only needs to build a reaction unit, a slight aromatization unit and a separation unit A for preparing aromatic hydrocarbon from methanol, and does not need to additionally build a new aromatic hydrocarbon conversion and separation unit, thereby greatly reducing the equipment investment, improving the overall technical competitiveness of a project and obtaining better technical effects.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
In FIG. 1, 101 is methanol; 102 is a methanol aromatization product; 103 is a gas phase; 104 is an oil phase; 105 is an aqueous phase; 106 is a non-aromatic stream; 107 is a first aromatic hydrocarbon stream; 108 is a light hydrocarbon stream; 109 is a second aromatic hydrocarbon stream; 110 is a light hydrocarbon aromatization product; 111 is a combustible gas.
The device comprises a methanol-to-aromatics unit, a light hydrocarbon aromatization unit, a first separation unit, a second separation unit and a third separation unit.
The process is briefly described as follows: methanol is converted into a methanol aromatization product through a methanol-to-aromatics unit; the methanol aromatization product is separated into a gas phase, an oil phase and a water phase in a first separation unit A; the oil phase is separated into a non-aromatic material flow and a first aromatic material flow through a second separation unit B; the non-aromatic material flow and the gas phase are sent to a third separation unit C to be separated into combustible gas, light hydrocarbon flow and second aromatic material flow; the light hydrocarbon material flow is converted into a light hydrocarbon aromatization product through a light hydrocarbon aromatization unit; the light hydrocarbon aromatization product returns to the third separation unit C; and sending the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow into an aromatic hydrocarbon integrated device for treatment.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
4.6 tons/hr of methanol feed is provided and reacted in the methanol aromatization reactor in contact with the ZSM-5 metal modified molecular sieve. The methanol aromatization reaction temperature is 550 ℃, the reaction pressure is 0.2MPA, and the reaction mass space velocity is 1.5hr-1. The conversion rate of methanol is 99.99%, the selectivity of carbon-based aromatic hydrocarbon is 50%, the selectivity of BTX in aromatic hydrocarbon is 78%, the mass content of benzene in BTX is 1.9%, the mass content of toluene is 19%, and the mass content of xylene is 79.1%. In a reaction product heat exchange cooler, the methanol aromatization product exchanges heat with medium-pressure saturated water to generate medium-pressure steam and recover reaction heat. The temperature of the methanol aromatization product at the outlet of the reaction product heat exchange cooler is 220 ℃. The methanol aromatization product carries out contact heat exchange with cooling water at 40 ℃ in a quenching tower, so that the gas phase temperature at the top of the tower is 40 ℃, and the temperature of an oil-water mixture at the bottom of the tower is 110 ℃. The oil-water mixture is cooled to 40 ℃, then sent into an oil-water separator, and separated into an oil phase and a water phase by a gravity type liquid-liquid separator. And (4) stripping the water phase to remove the oxygen-containing compound impurities in the water phase, and discharging the water phase out of the system. And separating the oil phase into a non-aromatic material flow and a first aromatic material flow through a depentanizer, wherein the mass content of benzene in the first aromatic material flow is 1.5%, the mass content of toluene is 14.7%, and the mass content of xylene is 61.2%. The gas phase from the top of the quenching tower is pressurized to 2MPa by a compressor and then sent to an absorption and desorption system, and aromatic hydrocarbon is used as an absorbent to absorb part of the carbon two components and all the carbon three or more components. The absorption tail gas contains hydrogen, methane, ethane and ethylene and is discharged out of the system as combustible gas. The desorbed light hydrocarbon stream contains hydrogen, methane and ethane with a total mass content of 0.05%. The light hydrocarbon material flow and the non-aromatic material flow from the depentanizer are sent into the light hydrocarbon aromaticThe reaction temperature is 520 ℃, the reaction pressure is 0.5MPA, and the reaction mass space velocity is 1hr-1. The light hydrocarbon aromatization product returns to the absorption desorption system. The aromatic hydrocarbon produced by the aromatization reaction of the light hydrocarbon is separated in a desorption tower and is extracted from the tower bottom, namely a second aromatic hydrocarbon material flow. The total mass content of benzene and toluene in the second aromatic hydrocarbon material flow is 64.1%, and the mass content of xylene is 17.2%. After the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are converged, the mass content of BTX in the mixed material flow is 79%, and the proportion of benzene, toluene and xylene is 1: 2.1: 4.3.
[ example 2 ]
Following the conditions and procedures described in example 1, the following conditions were varied: the methanol aromatization reaction temperature is 520 ℃, the reaction pressure is 0.25MPA, and the reaction mass space velocity is 0.5hr-1. The aromatization reaction temperature of the light hydrocarbon is 500 ℃, the reaction pressure is 0.2MPA, and the mass space velocity of the reaction is 0.2hr-1. After the gas phase at the top of the quenching tower is pressurized by a compressor to 3MPa, hydrogen, methane and ethane are separated by deep cooling to be used as combustible gas. The light hydrocarbons of ethylene, carbon three and below and non-aromatic substance flow are combined into light hydrocarbon substance flow, and the total mass content of hydrogen, methane and ethane in the light hydrocarbon substance flow is 0.01%. The light hydrocarbon material flow is sent into a light hydrocarbon aromatization reactor for reaction. And (3) rectifying and separating the light hydrocarbon aromatization product to obtain aromatic hydrocarbon as a second aromatic hydrocarbon material flow, extracting from the tower bottom, pressurizing the tower top by a compressor, and returning to the inlet of the light hydrocarbon aromatization reactor. The first aromatic hydrocarbon material flow obtained under the above conditions had a benzene mass content of 1.3%, a toluene mass content of 12.5%, a xylene mass content of 62.4%, a benzene toluene mass content of 66.8%, and a xylene mass content of 19.8%. After the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are converged, the mass content of BTX in the mixed material flow is 80%, and the ratio of benzene to toluene to xylene is 1:2: 4.4.
[ example 3 ]
Following the conditions and procedures described in example 1, the following conditions were varied: the methanol aromatization reaction temperature is 480 ℃, the reaction pressure is 0.15MPA, and the reaction mass space velocity is 0.6hr-1. The aromatization reaction temperature of light hydrocarbon is 650 deg.C, reaction pressure is 0.8MPA, and reaction mass space velocity is 2.5hr-1. Urgency of emergencyAfter the gas phase at the top of the cooling tower is pressurized by a compressor to 3.6MPa, firstly, hydrogen is obtained by adopting membrane separation, and then methane and ethane are separated by adopting cryogenic cooling to be used as combustible gas. The light hydrocarbons of ethylene, carbon three and below and non-aromatic substance flow are combined into light hydrocarbon substance flow, and the total mass content of hydrogen, methane and ethane in the light hydrocarbon substance flow is 0.7%. The light hydrocarbon material flow is sent into a light hydrocarbon aromatization reactor for reaction. And (3) rectifying and separating the light hydrocarbon aromatization product to obtain aromatic hydrocarbon as a second aromatic hydrocarbon material flow, extracting from the tower bottom, pressurizing the tower top by a compressor, and returning to the inlet of the light hydrocarbon aromatization reactor. The first aromatic hydrocarbon stream obtained under the above conditions had a benzene mass content of 2.4%, a toluene mass content of 13.8%, a xylene mass content of 61.9%, a benzene toluene mass content of 53.6%, and a xylene mass content of 16.4%. After the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are converged, the mass content of BTX in the mixed material flow is 75%, and the ratio of benzene, toluene and xylene is 1:2.2: 4.9.
[ example 4 ]
Following the conditions and procedures described in example 1, the following conditions were varied: the methanol aromatization reaction temperature is 460 ℃, the reaction pressure is 0.25MPA, and the reaction mass space velocity is 0.5hr-1. The aromatization reaction temperature of the light hydrocarbon is 550 ℃, the reaction pressure is 0.2MPA, and the mass space velocity of the reaction is 0.2hr-1. After the gas phase at the top of the quenching tower is pressurized by a compressor to 3.5MPa, hydrogen, methane and ethane are separated by cryogenic cooling to be used as combustible gas. The light hydrocarbons of ethylene, carbon three and below and non-aromatic substance flow are combined into light hydrocarbon substance flow, and the total mass content of hydrogen, methane and ethane in the light hydrocarbon substance flow is 0.5%. The light hydrocarbon material flow is sent into a light hydrocarbon aromatization reactor for reaction. And (3) rectifying and separating the light hydrocarbon aromatization product to obtain aromatic hydrocarbon as a second aromatic hydrocarbon material flow, extracting from the tower bottom, pressurizing the tower top by a compressor, and returning to the inlet of the light hydrocarbon aromatization reactor. The first aromatic hydrocarbon stream obtained under the above conditions had a benzene mass content of 1.2%, a toluene mass content of 11.9%, a xylene mass content of 58.7%, a benzene toluene mass content of 61.9%, and a xylene mass content of 18.6%. After the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are converged, the mass content of BTX in the mixed material flow is 75%, and the proportion of benzene, toluene and xylene is 1:2:4.5。
[ example 5 ]
Following the conditions and procedures described in example 1, the following conditions were varied: the methanol aromatization reaction temperature is 550 ℃, the reaction pressure is 0.2MPA, and the reaction mass space velocity is 1.5hr-1. The aromatization reaction temperature of the light hydrocarbon is 560 ℃, the reaction pressure is 0.3MPA, and the mass space velocity of the reaction is 0.3hr-1. After the gas phase at the top of the quenching tower is pressurized by a compressor to 3.5MPa, hydrogen, methane and ethane are separated by cryogenic cooling to be used as combustible gas. The light hydrocarbons of ethylene, carbon three and below and non-aromatic substance flow are combined into light hydrocarbon substance flow, and the total mass content of hydrogen, methane and ethane in the light hydrocarbon substance flow is 0.1%. The light hydrocarbon material flow is sent into a light hydrocarbon aromatization reactor for reaction. And (3) rectifying and separating the light hydrocarbon aromatization product to obtain aromatic hydrocarbon as a second aromatic hydrocarbon material flow, extracting from the tower bottom, pressurizing the tower top by a compressor, and returning to the inlet of the light hydrocarbon aromatization reactor. The first aromatic hydrocarbon stream obtained under the above conditions had a benzene mass content of 1.5%, a toluene mass content of 14.7%, a xylene mass content of 61.2%, a benzene toluene mass content of 62.2%, and a xylene mass content of 17.6%. After the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are converged, the mass content of BTX in the mixed material flow is 78%, and the ratio of benzene, toluene and xylene is 1:2.2: 4.5.
[ example 6 ]
Following the conditions and procedures described in example 1, the following conditions were varied: the methanol aromatization reaction temperature is 580 ℃, the reaction pressure is 0.4MPA, and the reaction mass space velocity is 0.6hr-1. The aromatization reaction temperature of the light hydrocarbon is 580 ℃, the reaction pressure is 0.25MPA, and the mass space velocity of the reaction is 0.35hr-1. After the gas phase at the top of the quenching tower is pressurized by a compressor to 3.0MPa, hydrogen, methane and ethane are separated by cryogenic cooling to be used as combustible gas. The light hydrocarbons of ethylene, carbon three and below and non-aromatic substance flow are combined into light hydrocarbon substance flow, and the total mass content of hydrogen, methane and ethane in the light hydrocarbon substance flow is 0.9%. The light hydrocarbon material flow is sent into a light hydrocarbon aromatization reactor for reaction. And (3) rectifying and separating the light hydrocarbon aromatization product to obtain aromatic hydrocarbon as a second aromatic hydrocarbon material flow, extracting from the tower bottom, pressurizing the tower top by a compressor, and returning to the inlet of the light hydrocarbon aromatization reactor. Obtained under the above conditionsThe mass content of benzene in the first aromatic hydrocarbon stream was 1.3%, the mass content of toluene was 8.8%, the mass content of xylene was 56.5%, the mass content of benzene in the second aromatic hydrocarbon stream was 57.8%, and the mass content of xylene was 19.7%. After the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow are converged, the mass content of BTX in the mixed material flow is 70%, and the ratio of benzene to toluene to xylene is 1:1.9: 4.7.
Claims (12)
1. A process method for preparing aromatic hydrocarbon and combustible gas by methanol comprises the following steps: 1) methanol is converted into a methanol aromatization product through a methanol-to-aromatics unit; 2) the methanol aromatization product is separated into a gas phase, an oil phase and a water phase in a first separation unit; 3) separating the oil phase into a non-aromatic stream and a first aromatic stream by a second separation unit; 4) the non-aromatic material flow and the gas phase are sent to a third separation unit to be separated into combustible gas, light hydrocarbon flow and second aromatic material flow; 5) the light hydrocarbon material flow is converted into a light hydrocarbon aromatization product through a light hydrocarbon aromatization unit; 6) and returning the light hydrocarbon aromatization product to the third separation unit, and sending the first aromatic hydrocarbon material flow and the second aromatic hydrocarbon material flow to an aromatic hydrocarbon integrated device for treatment.
2. The process for preparing aromatic hydrocarbon and combustible gas by methanol according to claim 1, wherein the methanol aromatization reaction conditions are as follows: the reaction temperature is 450-600 ℃, the reaction pressure is 0.1-0.5 MPa, and the reaction mass airspeed is 0.5-4 hr-1。
3. The process for preparing aromatic hydrocarbon and combustible gas from methanol according to claim 2, wherein the light hydrocarbon aromatization reaction conditions are as follows: the reaction temperature is 500-650 ℃, the reaction pressure is 0.1-1 MPa, and the reaction mass airspeed is 0.1-3 hr-1。
4. The process of claim 1, wherein the first aromatic stream has a benzene content of no greater than 5% by mass.
5. The process for producing aromatic hydrocarbons and combustible gases from methanol according to claim 1, wherein the xylene content of the first aromatic hydrocarbon stream is greater than 50% by mass fraction.
6. The process for producing aromatic hydrocarbons and combustible gases from methanol according to claim 1, wherein the xylene content of the first aromatic hydrocarbon stream is greater than 60% by mass fraction.
7. The process of claim 1, wherein the second aromatic stream has a xylene content of no greater than 25% by mass.
8. The process of claim 1, wherein the second aromatic stream has a benzene and toluene content of greater than 40% by mass.
9. The process of claim 1, wherein the second aromatic stream has a benzene and toluene content of greater than 50% by mass.
10. The process of claim 1, wherein the total weight of hydrogen, methane and ethane in the light hydrocarbon stream is less than 1%.
11. The process of claim 10, wherein the total weight of hydrogen, methane and ethane in the light hydrocarbon stream is less than 0.1%.
12. The process for producing aromatic hydrocarbons and combustible gas from methanol according to claim 1, wherein the combustible gas comprises hydrogen, methane and ethane.
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